Coordination Compounds MODULE - 6

Chemistry of Elements

24
24 COMPOUNDS
COORDINATION
Notes

You have come across compounds like Na[Ag(CN) ] and Na [Zn(CN) ]. Such compounds
2 2 4
are referred to as coordination compounds or complex compounds. Coordination compounds
play an important role in the chemical industry and in life itself. For example, the Ziegler-
Natta catalyst which is used for polymerization of ethylene, is a complex containing the
metals aluminum and titanium. Metal complexes play important role in biological systems.
For example, chlorophyll, which is vital for photosynthesis in plants, is a magnesium complex
and heamoglobin, which carries oxygen to animal cells, is an iron complex. These are the
compounds that contain a central atom or ion, usually a metal, surrounded by a number of
ions or molecules. The complexes tend to retain their identity even in solution, although
partial dissociation may occur. Complex ion may be cationic, anionic or nonionic, depending
on the sum of the charges of the central atom and the surrounding ions and molecules.
In this lesson you will study about the complexes including their nomenclature and nature
of bonding in them.

Objectives
After reading this lesson, the learner will be able to,

 state the postulates of Werner’s theory;

 define ligands, coordination number and coordination sphere;

 name simple complexes by IUPAC system;

 explain valance bond theory;

 apply VB theory to explain hybridization, shape and magnetic behavior of the following
complexes [Fe(CN) 6] 4–, [Fe(CN) 6] 3–, [Cr(NH 3) 6] 2+, [NiCl 4] 2-, [Ni(CO) 4] and
[Ni(CN)4]2– and

 explain the applications of coordination compounds in extraction of metals, medicine

and qualitative analysis.
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24.1 Werners’ Coordination Theory
Coordination compounds were known in eighteenth century. It was a mystery for the
chemist, of those days to understand as to why a stable salt like CoCl3 reacts with varying
number of stable molecules or compounds such as ammonia to give several new compounds:
CoCl 3.6NH 3, CoCl 3.5NH 3 and CoCl 3.4NH 3; and what are their structures? These
compounds differed from each other in their chloride ion reactivity. Conductivity
Notes
measurements on solutions of these compounds showed that the number of ions present in
solution for each compound are different. Several theories were proposed, but none could
satisfactorily explain all the observable properties of these compounds and similar other
series of compounds which had been prepared by then. It was only in 1893 that Werner
put forward a set of ideas which are known as Werner’s coordination theory, to explain
the nature of bonding in complexes. His theory has been a guiding principle in inorganic
chemistry and in the concept of valence. The important postulates of Werner’s theory
are:
1. Metals exhibit two types of valence:
(a) Primary valence (ionizable)
(b) Secondary valence (non-ionizable).
Primary or ionizable valence is satisfied by negative ions and corresponds to oxidation
state of the metal. The secondary or non-ionizable valence, which is satisfied by negative,
positive or neutral groups, is equal to the coordination number of metal ion.
Every metal tends to satisfy both its primary and secondary valence.
2. The secondary valence is directed toward fixed positions in space i.e. this has spatial
arrangement corresponding to different coordination number.
For the complexes CoCl3.6NH3 CoCl3.5NH3 and CoCl3.4NH3, the number of ionizable
ions in these complexes are three, two and one, respectively. It has been proved by
precipitation reactions and conductivity measurements. On the basis of Werner’s postulate
these compounds are formulated as:
[Co(NH3)6]Cl3 , [Co(NH3)5Cl]Cl2 and [Co(NH3)4Cl2]Cl, respectively, the species inside
the square brackets being the complex ion and outside the square brackets the ionisable
ions.
On the basis of Werner’s theory the structure of [Co(NH3)5Cl] Cl2 is:

Cl
H3N
NH3
Co

H3N NH3
Cl Cl
NH3
Primary valance (ionizable)(--------)
Secondary valance (non-ionizable) (––––––)
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One of the three chloride ions satisfy both primary and secondary valence.
He also postulated that octahedral, tetrahedral and square planar shapes are more common
for coordination compounds of transition elements. Six coordinated complexes such as
[Ni(NH3)6]2+ and [Co(NH3)6]3+ are octahedral whereas four coordinated such as [NiCl4]2-
and [Ni(CN)4]2- are tetrahedral and square planar, respectively.
Notes
Intext Questions 24.1
1. Explain primary valence.
................................................................................................................................
2. Explain secondary valence.
................................................................................................................................
3. What is the number of the secondary valence in the following: [Cr(H2O)6] Cl3 and
[Co(NH3)5Cl]Cl2 ?
................................................................................................................................
4. What is shape associated with a six-coordinated complex?
................................................................................................................................
5. How many types of shapes are possible for four-coordinate complexes?
................................................................................................................................

24.2 Definition of Some Important Terms

There are certain terms, which are normally used in dealing with coordination compounds.
Some of these important terms are defined below:
Ligand: the molecules or ions that are attached to the metal in a complex ion are called
ligands. The interaction between a metal atom and the ligands can be thought of as Lewis
acid-base reaction. As you know a Lewis base is a substance capable of donating one or
more electron pairs, every ligand has at least one unshared pair of valence electron. Few
examples are shown below:
:O: ..
N .. –
[ : :
H H H H .. ]
Cl
H

The atom in the ligand that is bound directly to the metal atom is known as the donor atom.
For example, nitrogen is the donor atom and Cu2+ is the acceptor atom in the [Cu(NH3)4]2+
complex ion.
Depending on the number of the donor atoms present, ligands are defined as monodentate,
bidentate or polydentate. H2O and NH3 are monodentate ligands with only one donor
atom in each. Ethylenediamine (en) is a bidentate ligand.
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H2N NH2

CH2 CH2
Notes Ethylenediamine

The two nitrogen atoms can coordinate with a metal atom. Bidentate and polydentate
ligands are also called chelating agents because of their ability to hold the metal
atom like a claw (from the Greek Chele, meaning “claw”) one example is
ethylenediaminetetraacetate ion (EDTA), a polydentate (hexadentate) ligand.

O O

OC CH2 CH2 CO
N CH2 CH2 N
OC CH2 CH2 CO

O O
Ethylenediaminetetraccetate ion

Coordination number: The coordination number in coordination compounds is defined

as the number of ligand (donor) atoms/ions surrounding the central metal atom in a complex
ion. For example, the coordination number of cobalt in [Co(NH3)6]3+ is six. Similarly the
coordination number of Ag+ in [Ag(NH3)2]+ is 2, that of Cu2+ in [Cu(NH3)4]2+ is 4, and
that of Fe3+ in [Fe(CN)6]3– is 6.

Coordination sphere: The central metal atom and the ligands which are directly attached
to it are enclosed in a square bracket and are collectively termed as coordination sphere.
The ligands and the metal atom inside the square brackets behave as single constituent
unit.

  
[Cr(NH 3 )4 Cl 2 ] Cl
Coordination sphere

Oxidation number: Another important property of coordination compounds is the

oxidation number of the central metal atom. The net charge on a complex ion is the sum of
the charges on the central atom and its surrounding ligands. In the [PtCl6]2- ion for example,
each chloride ion has an oxidation number of –1, so the oxidation number of Pt must be
+4. If the ligands do not bear net charges the oxidation number of the metal is equal to the
charge of the complex ion. Thus in [Cu(NH3)4]2+ each NH3 is neutral, so the oxidation
number of copper is +2.

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Intext Questions 24.2
1. What is the coordination number of the metal ion in the following?
(i) [Co(NH3)5Cl]+
(ii) [Cr(en)2Cl2]+
Notes
(iii) [NiCl4]2-
................................................................................................................................
2. What is the oxidation state of the metal ion in the following?
(i) [MnCl6]4-
(ii) [Fe(CN)6]3-
(iii) [Cr(NH3) 6]3+
(iv) [Ni(en)3]2+
................................................................................................................................
3. Give an example of a chelate ligand.
................................................................................................................................
4. Give one example of each monodentate, bidentate and polydenatate ligand.
................................................................................................................................
5. what is the oxidation and coordination number of Co in this [Co(en) 2(H2O)CN]2+
complex ion Which ligand is bidentate in the above complex?
................................................................................................................................

24.3 Rules of Nomenclature of Coordination Compounds

We have already discussed about the ligands and oxidation number of metal, our next step
is, to learn how to name these coordination compounds. The rules for naming coordination
compounds as recommended by IUPAC are as follows:
1. The cation is named before the anion, as in other ionic compounds. The rule holds
regardless of whether the complex ion bears a net positive or a negative charge. For
example, in K3[Fe(CN)6] and [Co(NH3)4Cl2]Cl compound, we name the K+ and
[Co(NH3)4Cl2]+ first, respectively.
2. Within a complex ligands are named first, in alphabetical order, and the metal ion is
named last.
3. The name of anionic ligand ends with the letter ‘O’, whereas a neutral ligand is
usually called by the name of the molecule. The exceptions are H2O (aqua), CO
(carbonyl) and NH3 (ammine). The table given below lists some common ligands:

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Table 24.1 : Some Common Ligands
Ligand Name of the ligand in coordination
compounds
–
Fluoride (F ) Fluro
–
Chloride (Cl ) Chloro
Bromide (Br– ) Bromo
Notes Hydroxide (OH– ) Hydroxo
Sulphate (SO42–) Sulphato
Oxide (O2–) Oxo
Carbonate (CO32–) Carbonato
Oxalate (C2O42–) Oxalato
Thiocyanate (SCN– ) Thiocyanato
Cyanide (CN– ) Cyano
Isothiocyanate (NCS– ) Isothiocyanato
Ethylenediamine (NH2CH2CH2NH2) Etylenediamine
Ammonia (NH3 ) Ammine
Water (H2O) Aqua
Carbon monoxide (CO) Carbonyl
EDTA Ethylenediamineteracetato

4. When several ligands of a particular kind are present, we use the Greek prefix di, tri-
tetra etc to name them. Thus the ligands in cation [Co(NH3)4Cl2]+ are named as
“tetraammine dichloro” (note that prefixes are ignored when alphabetizing ligands).
If the ligand itself contains a Greek prefix, we use the prefixes bis,tris and tetrakis
etc to indicate the number of ligands present. For example, the ligand ethylenediamine
already contains di, therefore, if two such ligands are present the name is
bis(ethylenediamine).
5. The oxidation number of the metal is written in roman numerals following the
name of the metal. For example, the roman numeral III is used to indicate the
+3 oxidation state of chromium in [Cr(NH 3 ) 4 Cl 2 ] + , which is named as
tetraamminedichlorochromium (III) ion.
6. If the complex is an anion, its name ends in –ate. For example, in K 4[Fe(CN)6] the
anion [Fe(CN)6]4– is called hexacyanoferrate(II) ion. Note that the numeral (II) indicate
the oxidation state of iron. Table given below gives tha name of anions containing
metal atoms.
7. If the complex is either a cation or is neutral, no change is required in the name of
the central metal ion. For example [Co(NH 3)6]3+ and [Ni(CO) 4] are named as
hexaamminecobalt(III)ion and tetracarbonyl nickel(0), respectively.
Table 2.4 : Some anions containing metal atoms
Metal Name of metal in anionic state
Copper Cuperate
Zinc Zincate
Aluminum Aluminate
Chromium Chromate
Tin Stannate
Cobalt Cobaltate
Nickel Nickelate
Gold Aurate
Silver Argentate
Lead Plumbate
Rhodium Rhodate
Iron Ferrate
Manganese Manganate
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A. few examples are given below:
[Co(H2O)6]Cl3 hexaaquacobalt(III) chloride
K2[PtCl6] potassium hexachloroplatinate(IV)
[Pt(NH3)2Cl4] diamminetetrachloroplatinum(IV)
[Co(en)2Cl2]Cl dichlorobis (ethylenediamine)cobalt(III) chloride. Notes

Intext Questions 24.3

1. Write down the name of the following complexes:
(a) [Co(NH3)4Cl2]+
(b) (NH4)3[Cr(NCS)6]
(c) Ni(CO)4
(d) K4[Fe(CN)6]
(e) [Cr(en)3]Cl3
................................................................................................................................
2. Write down the formula of the following:
(a) Tetrachloronickelate(II)
(b) Pentaamminenitrocobalt(III) ion
c) Potassium hexacyanoferrate(III)
d) Dichlorobis(ethylenediammine) chromium(III) ion
...............................................................................................................................

24.4 Valence Bond Theory

Linus Pauling of the California Institute of Technology developed the valance bond theory.
He was awarded the Nobel prize in chemistry in 1954. Pauling’s ideas have had an important
impact on all areas of chemistry. He applied valence bond theory to coordination compounds.
This theory can account reasonably well for the structure and magnetic properties of
metal complexes.
The basic principles, which are involved in the valence bond treatment of coordination
compounds are:
(a) Hybridization of valance orbitals of the central metal/ ion
(b) Bonding between ligand and the metal ion/atom.
(c) Relation between the type of bond and the observed magnetic behaviour.
Six Coordinate Complexes
Let us explain by taking simple examples such as [CoF6]3- and [Co(NH3)6]3+. Although in
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Chemistry of Elements both the complexes, the oxidation state of cobalt is +3, but [CoF6]3- is paramagnetic and
[Co(NH3)6]3+ is diamagnetic, why? The formation of a complex may be considered as a
series of hypothetical steps. First the appropriate metal ion is taken e.g. Co3+. Cobalt atom
has the outer electronic configuration 3d74s2. Thus Co3+ ion will have the configuration
3d6 and the electrons will be arranged as:
3d 4s 4p
Notes

+3
Co ion forms both paramagnetic (outer orbital) and diamagnetic (inner orbital)
complexes depending upon the nature of ligands as illustrated below.
As Co3+ ion combines with six fluoride ligands in [CoF6]3–, empty atomic orbitals are
required on the metal ion to receive the coordinated lone pair of electrons. The orbitals
used are one 4s, three 4p and two 4d. These are hybridized to give a set of six equivalent
sp3d2 hybrid orbitals. A ligand orbital containing a lone pair of electron forms a coordinate
bond by overlapping with an empty hybrid orbital on the metal ion. In this way a  bond is
formed with each ligand. The d-orbitals used are the 4d 2 2 and 4d z 2 . It is shown
x y
below:

3d 4s 4p 4d
** ** ** ** ** **
– – –
F F– F– F– F F
sp3d 2, outer orbital complex

Since the outer 4d orbitals are used for bonding, this is called an outer orbital complex. The
energy of these orbitals is quite high, so the complex will be reactive. This complex will be
high-spin paramagnetic, because it has four unpaired electrons.
An alternative octahedral arrangement in [Co(NH3)6]3+ is possible when the electrons on
metal ion are rearranged as shown below:
3d 4s 4p

** ** ** ** ** **

NH3 NH3 NH3 NH3 NH3 NH3

d 2sp3 , inner orbital complex

Since inner d-orbitals are used this is called an inner orbital complex. There is no unpaired
electron, the complex will be low-spin diamagnetic.
The metal ion can also form 4-coordinate complexes. For such complexes two different
arrangements are possible i.e. tetrahedral (sp3) and square planar (dsp2):
3d 4s 4p
** ** ** **
tetrahedral sp3
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3d 4s 4p
** ** **
square planar dsp2

About such complexes you will study later.

Notes
Let us illustrate six coordinate complexes with more examples:
1. Cr(NH3) 6] 3+
The electronic configuration of only 3d, 4s and 4p orbitals are taken into account. The
following steps are involved. The electronic configuration of Cr atom and Cr 3+ ion are
given in (i) and (ii) below:
(i) Cr ground state:

3d 4s 4p

(ii) Cr 3+

3d 4s 4p

(iii) [Cr(NH3)6]3+

3d 4s 4p

** ** ** ** ** **
NH3NH3 NH3 NH3 NH3 NH3
d2sp3 (inner orbital)
The 12 electrons for bond formation come from six ligands, each donating a lone pair of
electrons. The resulting complex will be paramagnetic because it has three unpaired
electrons. Its magnetic moment will be:
n ( n  2)  3( 3  2)  15  3.87B.M
2. [Fe(CN)6]4-
(i) Fe
3d 4s 4p

(ii) Fe 2+
3d 4s 4p

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(iii) [Fe(CN)6]4–
3d 4s 4p

** ** ** ** ** **
– – –
–
CN CN
–
CN CN– CN CN

Notes d2sp3
The resulting complex is inner orbital, octahedral and due to the absence of unpaired
electron, it will be diamagnetic.
3. [Fe(CN)6]3-
(i) Fe
3d 4s 4p

(ii) Fe 3+
3d 4s 4p

(iii) [Fe(CN)6]3–
3d 4s 4p
** ** ** ** ** **
– – –
– –
CN CN CN CN– CN CN
d 2sp 3
The resulting complex is inner orbital, octahedral. Due to presence of one unpaired electron,
it will be paramagnetic.
Four coordinate complexes:
1. [NiCl4]2-
(i) Ni
3d 4s 4p

(ii) Ni2+
3d 4s 4p

(iii) [NiCl4]2–
3d 4s 4p
** ** ** **
– – –
Cl Cl Cl– Cl

110 sp3
 Coordination Compounds MODULE - 6
Chemistry of Elements
The resulting complex will be tetrahedral with two unpaired electrons. It will be paramagnetic.
2. Ni(CO)4
(i) Ni
3d 4s 4p
Notes
(ii) Ni(O)
3d 4s 4p

(iii) Ni(CO)4

3d 4s 4p
** ** ** **
CO CO CO CO
sp 3
The resulting complex will be tetrahedral. It has no unpaired electrons and will be
diamagnetic.

3. [Ni(CN)4]2-

(i) Ni

3d 4s 4p

(ii) Ni2+

3d 4s 4p

(iii) [Ni(CN)4]2-

3d 4s 4p

** ** ** **
CN –
CN –
CN– CN–

dsp2

The resulting complex is square planar and diamagnetic.

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Intext Questions 24.4
1. Name the type of hybridization present in: [Co(NH3)6]3+..
................................................................................................................................
2. [Fe(CN)6]3– is diamagnetic or paramagnetic?
Notes
................................................................................................................................
3. [NiCl4]2– and Ni(CO)4 have sp3 or dsp2 hybridization?
................................................................................................................................
4. Which one is diamagnetic: [Ni(CN)4]2– or [NiCl4]2–?
................................................................................................................................
5. What type of hybridization is shown by (i) inner and (ii) outer orbital complexes?
................................................................................................................................

24.5 Applications of Coordination Compounds

Coordination compounds are found in living systems and have many uses in the home, in
industry and in medicines. A few examples are given below:
Extraction of metals: cyanide ions are used for the for the extraction of gold and silver.
The crushed ore is heated with an aq. cyanide solution in the presence of air to dissolve the
gold by forming the soluble complex ion [Au(CN)2]–.
4Au(s) + 8CN (aq) + O2(g) + 2H2O(l)  4[Au(CN)2] (aq) + 4 OH (aq)
– – –

Zn(s) + 2[Au(CN)2] (aq)  [Zn(CN)4]2– (aq) + 2Au(s)

–

Complex formation is also useful for the purification of metals. Nickel is purified by
converting the metal to the gaseous compound Ni(CO)4 and then decomposing the latter to
pure nickel.
Medicines: EDTA is a chelating agent which is used in the treatment of lead poisoning.
Cis platin cis [Pt(NH3)2Cl2] is used in the treatment of cancer. Sodium nitroprusside,
Na2[Fe(CN)5NO] is used to lower blood pressure during surgery.
Qualitative Analyses: complex formation is useful for qualitative analyses.
(a) Separation of Ag+ from Pb2+ & Hg2+
Ag+ + 2NH3(aq.)  [Ag(NH3)2]+
Soluble
(b) Separation of IIA and IIB groups: The cations of IIB group form soluble complex
with yellow ammonium sulphide.
(c) Cu2+ ion forms complex on addition of ammonia [Cu(NH3)4]2+.

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Chemistry of Elements
(d) Fe2+ forms a blue complex with K3Fe(CN)6, i.e. K FeII[FeIII(CN)6].
(f) Cobalt(II) gives color with HCl due to the formation of complex [CoCl4]2–.
(g) Nickel forms a red complex [Ni(DMG)2] with dimethylglyoxime (H2DMG).

Intext Questions 24.5 Notes

1. Name two elements which are extracted by complexation.
................................................................................................................................
2. What is the use of EDTA in medicine?
................................................................................................................................
3. Name the compound of platinum which is used as anticancer agent?
................................................................................................................................
4. Give two uses of complexes in qualitative analyses
................................................................................................................................

What You Have Learnt

 Coordination compounds are compound in which a central metal ion is attached to a
group of surrounding ligands by coordinate covalent bond. Ligands can be monodentate
or polydentate, depending upon the number of donor atoms attached to the metal.
Polydentate ligands are also called chelating agents. They form complexes that have
rings of atoms known as chelate rings.
 The number of donor atoms bonded to a metal is called the coordination number of
the metal. Common coordination number and geometries are 2 (linear), 4 (tetrahedral
and square planar), and 6 (octahedral).
 Systematic names for complexes specify the number of ligands of each particular
type, the metal, and its oxidation state.
 Valance Bond Theory describes the bonding in complexes in terms of two-electron,
coordinate covalent bonds resulting from the overlap of filled ligand orbitals with
vacant metal hybrid orbitals that point in the direction of the ligands; sp (linear), sp3
(tetrahedral), dsp2 (square planar) and d2sp3 or sp3d2 (octahedral).
 Complexes are very useful in qualitative analyses and in medicine.

Terminal Exercise
1. Define the following:
(i) Coordination number
(ii) Coordination sphere

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(iii) Oxidation number
2. Define ligands. Give one example of each of monodentate, bidentate and polydentate
ligands.
3. Write the postulates of Werner’s theory of coordination compounds.
4. Write down the name of the following complexes:
Notes
(i) K3[Cr(C 2O4)3]
(ii) [Co(NH3)2(H2O)2Cl2]+
(iii) [Pt(en)2]2+
(iv) [NiCl4]2–
(v) [Fe(CN)6]4–
5. Write down the formulae of the following complexes:
i. Tris(ethylenediamine)platinum(IV)
ii. Tetraaquadibromocobalt(III) ion
iii. Sodium tetraiodozincate(II)
iv. Tetracyanonickelate(II) ion
v. Dichlorotetrathiocyanatochromium(III) ion
6. Give the salient features of VB theory for complexes. What do you mean by inner
and outer orbital complexes?
7. [NiCl4]2– and Ni(CO)4 are tetrahedral but differ in magnetic behaviour, explain.
8. Ni(CO)4 and [Ni(CN)4]2– are diamagnetic but have different geometry, explain.
9. [NiCl4]2– is paramagnetic whereas [Ni(CN)4]2– is diamagnetic, explain.
10. Explain the types of hybridization and magnetic behaviour of the following complexes
on the basis of VB theory:
i. [Fe(CN)6]4–
ii. [Cr(NH3) 6]2+
iii. [Fe(CN)6]3–
iv. [NiCl4]2–
v. Ni(CO)4
11. Explain the application of complexes in extraction of elements, medicines and qualitative
analyses.

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Anwers to Intext Questions

24.1
1. Primary valence corresponds to the oxidation state of the central metal ion. It is
satisfied by negative ions only. Notes
2. Secondary valence of the metal corresponds to coordination number and is satisfied
by negative ions or neutral molecules.
3. In both secondary valance is 6.
4. Octahedral.
5. Two i.e. Tetrahedral or square planar.

24.2
1. (i) 6
(ii) 6
(iii) 4
2. (i) +2
(ii) +3
(iii) +3
(iv) +2
3. EDTA
4. NH3, ethylenediammine and EDTA
5. +3, 6, Ethylenediammine.

24.3
1. (i) Tetraamminedichlorocobalt(III) ion
(ii) Ammonium-hexaisothiocyanatochromate(III)
(iii) Tetracarbonylnickel(0)
(iv) Potassium-hexacyanoferrate(II)
(v) Tris(ethylenediamine)chromium(III) chloride
2. (i) [NiCl4]2–
(ii) [Co(NH3)5NO2]2+
(iii) K3[Fe(CN)6] –
(iv) [Cr(en)2Cl2]+
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24.4
1. d2sp3
2. [Fe(CN)6]3– is paramagnetic because it has one unpaired electron.
3. Both the complexes have sp3 (tetrahedral) hybridization.
Notes
4. [Ni(CN)4]2– is diamagnetic because it is square planar (dsp2 hybridization). It has no
unpaired electron.
5. Inner – d2sp3, outer – sp3d2

24.5
1. Gold and silver are extracted by cyanide process.
2. EDTA forms soluble complex with elements. It is used in the treatment of lead
poisoning.
3. Cis-platin
4. [Cu(NH3)4]2+ & [Ni(DMG)2]

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SENIOR SECONDARY COURSEMODULE - 6
Chemistry of Elements
CHEMISTRY
Student’s Assignment – 5

Notes 1
Maximum Marks: 50 Time : 1 Hours
2

INSTRUCTIONS
 Answer all the questions on a separate sheet of paper.
 Give the following information on your answer sheet:
 Name
 Enrolment Number
 Subject
 Assignment Number
 Address
 Get your assignment checked by the subject teacher at your study centre so that you get positive
feedback about your performance.

Do not send your assignment to NIOS

1. (a) Name the components of Bordeaux mixture.
(b) Define an ore.
(c) How is Flux related to Gangue and Slag?
(d) Define interstial compounds.
(e) Define paramagnetism.
(f) State two uses of sodium bicarbonate.
(g) What are Fullerenes?
(h) Name three isotopes of hydrogen.
(i) Write a chemical reaction showing the strong dehydrating property of sulphuric acid.
(j) Write a chemical reaction showing the formation of nitroglycerine from glycerine.
1 × 10 = 10
2. (a) Name the oxides of phosphorus and draw the structure of anyone of them.
(b) List four characteristics of p-block elements.
(c) Differenciate roasting from calcination.
(d) Defferenciate Electron affinity from Electronegativity.
(e) Despite being in different group lithium shows similarities with Magnesium. Explain.
(f) Hydrated ions of some transition elements appear coloured. Explain.
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 (g) Elements bearing atomic numbers from 21 to 30 are d-block elements which of them is not a
transition element and why?
(h) List 4 characteristics of Transition Metals.
(i) How is heavy water different from ordinary water?
(j) Draw angular resonance structure of nitric oxide. (2 × 10 = 20)
3. (a) Assign the geometry to the following molecules using the VSEPR theory. State reasons for your
answers.
(i) Phosphorus (V) Chloride (PCl5)
(ii) Sulphur (VI) Flouride (SF6)
(iii) Boron (III) Flouride (BF3).
(b) Potassium permanganate shows different chemical reactions in alkaline, neutral and acidic solutions.
Write one chemical each, showing the difference in behaviour.
(c) How purified Haemetite is converted into iron using the process of smelting. Write the chemical
equations involved.
(d) Write the sequence of chemical reactions involved in the production of washing soda using solvay
process. (3 × 4 = 12)
4. (a) In the table given below the ionization energy (in kJ mol–1) of some elements is shows against their
symbol with atomic number
Li
3 4
Be B
5 6
C 7
N 8
O 9
F 10
Ne
520 900 800 1090 1400 1310 1680 2080

Study the table carefully and explain why the increase in ionization potential is not steady as we
move from left to right.
(b) On the basis of the electronic configuration classify elements bearing atomic number 18, 26, 35
and 27 into the following groups.
(i) Alkaline earth metals
(ii) Noble gases
(iii) Halogens
(iv) Transition elements (4 × 2 = 8)
 Coordination Compounds MODULE - 6
Chemistry of Elements

24
24 COMPOUNDS
COORDINATION
Notes

You have come across compounds like Na[Ag(CN) ] and Na [Zn(CN) ]. Such compounds
2 2 4
are referred to as coordination compounds or complex compounds. Coordination compounds
play an important role in the chemical industry and in life itself. For example, the Ziegler-
Natta catalyst which is used for polymerization of ethylene, is a complex containing the
metals aluminum and titanium. Metal complexes play important role in biological systems.
For example, chlorophyll, which is vital for photosynthesis in plants, is a magnesium complex
and heamoglobin, which carries oxygen to animal cells, is an iron complex. These are the
compounds that contain a central atom or ion, usually a metal, surrounded by a number of
ions or molecules. The complexes tend to retain their identity even in solution, although
partial dissociation may occur. Complex ion may be cationic, anionic or nonionic, depending
on the sum of the charges of the central atom and the surrounding ions and molecules.
In this lesson you will study about the complexes including their nomenclature and nature
of bonding in them.

Objectives
After reading this lesson, the learner will be able to,

 state the postulates of Werner’s theory;

 define ligands, coordination number and coordination sphere;

 name simple complexes by IUPAC system;

 explain valance bond theory;

 apply VB theory to explain hybridization, shape and magnetic behavior of the following
complexes [Fe(CN) 6] 4–, [Fe(CN) 6] 3–, [Cr(NH 3) 6] 2+, [NiCl 4] 2-, [Ni(CO) 4] and
[Ni(CN)4]2– and

 explain the applications of coordination compounds in extraction of metals, medicine

and qualitative analysis.
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24.1 Werners’ Coordination Theory
Coordination compounds were known in eighteenth century. It was a mystery for the
chemist, of those days to understand as to why a stable salt like CoCl3 reacts with varying
number of stable molecules or compounds such as ammonia to give several new compounds:
CoCl 3.6NH 3, CoCl 3.5NH 3 and CoCl 3.4NH 3; and what are their structures? These
compounds differed from each other in their chloride ion reactivity. Conductivity
Notes
measurements on solutions of these compounds showed that the number of ions present in
solution for each compound are different. Several theories were proposed, but none could
satisfactorily explain all the observable properties of these compounds and similar other
series of compounds which had been prepared by then. It was only in 1893 that Werner
put forward a set of ideas which are known as Werner’s coordination theory, to explain
the nature of bonding in complexes. His theory has been a guiding principle in inorganic
chemistry and in the concept of valence. The important postulates of Werner’s theory
are:
1. Metals exhibit two types of valence:
(a) Primary valence (ionizable)
(b) Secondary valence (non-ionizable).
Primary or ionizable valence is satisfied by negative ions and corresponds to oxidation
state of the metal. The secondary or non-ionizable valence, which is satisfied by negative,
positive or neutral groups, is equal to the coordination number of metal ion.
Every metal tends to satisfy both its primary and secondary valence.
2. The secondary valence is directed toward fixed positions in space i.e. this has spatial
arrangement corresponding to different coordination number.
For the complexes CoCl3.6NH3 CoCl3.5NH3 and CoCl3.4NH3, the number of ionizable
ions in these complexes are three, two and one, respectively. It has been proved by
precipitation reactions and conductivity measurements. On the basis of Werner’s postulate
these compounds are formulated as:
[Co(NH3)6]Cl3 , [Co(NH3)5Cl]Cl2 and [Co(NH3)4Cl2]Cl, respectively, the species inside
the square brackets being the complex ion and outside the square brackets the ionisable
ions.
On the basis of Werner’s theory the structure of [Co(NH3)5Cl] Cl2 is:

Cl
H3N
NH3
Co

H3N NH3
Cl Cl
NH3
Primary valance (ionizable)(--------)
Secondary valance (non-ionizable) (––––––)
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 Coordination Compounds MODULE - 6
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One of the three chloride ions satisfy both primary and secondary valence.
He also postulated that octahedral, tetrahedral and square planar shapes are more common
for coordination compounds of transition elements. Six coordinated complexes such as
[Ni(NH3)6]2+ and [Co(NH3)6]3+ are octahedral whereas four coordinated such as [NiCl4]2-
and [Ni(CN)4]2- are tetrahedral and square planar, respectively.
Notes
Intext Questions 24.1
1. Explain primary valence.
................................................................................................................................
2. Explain secondary valence.
................................................................................................................................
3. What is the number of the secondary valence in the following: [Cr(H2O)6] Cl3 and
[Co(NH3)5Cl]Cl2 ?
................................................................................................................................
4. What is shape associated with a six-coordinated complex?
................................................................................................................................
5. How many types of shapes are possible for four-coordinate complexes?
................................................................................................................................

24.2 Definition of Some Important Terms

There are certain terms, which are normally used in dealing with coordination compounds.
Some of these important terms are defined below:
Ligand: the molecules or ions that are attached to the metal in a complex ion are called
ligands. The interaction between a metal atom and the ligands can be thought of as Lewis
acid-base reaction. As you know a Lewis base is a substance capable of donating one or
more electron pairs, every ligand has at least one unshared pair of valence electron. Few
examples are shown below:
:O: ..
N .. –
[ : :
H H H H .. ]
Cl
H

The atom in the ligand that is bound directly to the metal atom is known as the donor atom.
For example, nitrogen is the donor atom and Cu2+ is the acceptor atom in the [Cu(NH3)4]2+
complex ion.
Depending on the number of the donor atoms present, ligands are defined as monodentate,
bidentate or polydentate. H2O and NH3 are monodentate ligands with only one donor
atom in each. Ethylenediamine (en) is a bidentate ligand.
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 MODULE - 6 Chemistry

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H2N NH2

CH2 CH2
Notes Ethylenediamine

The two nitrogen atoms can coordinate with a metal atom. Bidentate and polydentate
ligands are also called chelating agents because of their ability to hold the metal
atom like a claw (from the Greek Chele, meaning “claw”) one example is
ethylenediaminetetraacetate ion (EDTA), a polydentate (hexadentate) ligand.

O O

OC CH2 CH2 CO
N CH2 CH2 N
OC CH2 CH2 CO

O O
Ethylenediaminetetraccetate ion

Coordination number: The coordination number in coordination compounds is defined

as the number of ligand (donor) atoms/ions surrounding the central metal atom in a complex
ion. For example, the coordination number of cobalt in [Co(NH3)6]3+ is six. Similarly the
coordination number of Ag+ in [Ag(NH3)2]+ is 2, that of Cu2+ in [Cu(NH3)4]2+ is 4, and
that of Fe3+ in [Fe(CN)6]3– is 6.

Coordination sphere: The central metal atom and the ligands which are directly attached
to it are enclosed in a square bracket and are collectively termed as coordination sphere.
The ligands and the metal atom inside the square brackets behave as single constituent
unit.

  
[Cr(NH 3 )4 Cl 2 ] Cl
Coordination sphere

Oxidation number: Another important property of coordination compounds is the

oxidation number of the central metal atom. The net charge on a complex ion is the sum of
the charges on the central atom and its surrounding ligands. In the [PtCl6]2- ion for example,
each chloride ion has an oxidation number of –1, so the oxidation number of Pt must be
+4. If the ligands do not bear net charges the oxidation number of the metal is equal to the
charge of the complex ion. Thus in [Cu(NH3)4]2+ each NH3 is neutral, so the oxidation
number of copper is +2.

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Intext Questions 24.2
1. What is the coordination number of the metal ion in the following?
(i) [Co(NH3)5Cl]+
(ii) [Cr(en)2Cl2]+
Notes
(iii) [NiCl4]2-
................................................................................................................................
2. What is the oxidation state of the metal ion in the following?
(i) [MnCl6]4-
(ii) [Fe(CN)6]3-
(iii) [Cr(NH3) 6]3+
(iv) [Ni(en)3]2+
................................................................................................................................
3. Give an example of a chelate ligand.
................................................................................................................................
4. Give one example of each monodentate, bidentate and polydenatate ligand.
................................................................................................................................
5. what is the oxidation and coordination number of Co in this [Co(en) 2(H2O)CN]2+
complex ion Which ligand is bidentate in the above complex?
................................................................................................................................

24.3 Rules of Nomenclature of Coordination Compounds

We have already discussed about the ligands and oxidation number of metal, our next step
is, to learn how to name these coordination compounds. The rules for naming coordination
compounds as recommended by IUPAC are as follows:
1. The cation is named before the anion, as in other ionic compounds. The rule holds
regardless of whether the complex ion bears a net positive or a negative charge. For
example, in K3[Fe(CN)6] and [Co(NH3)4Cl2]Cl compound, we name the K+ and
[Co(NH3)4Cl2]+ first, respectively.
2. Within a complex ligands are named first, in alphabetical order, and the metal ion is
named last.
3. The name of anionic ligand ends with the letter ‘O’, whereas a neutral ligand is
usually called by the name of the molecule. The exceptions are H2O (aqua), CO
(carbonyl) and NH3 (ammine). The table given below lists some common ligands:

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Table 24.1 : Some Common Ligands
Ligand Name of the ligand in coordination
compounds
–
Fluoride (F ) Fluro
–
Chloride (Cl ) Chloro
Bromide (Br– ) Bromo
Notes Hydroxide (OH– ) Hydroxo
Sulphate (SO42–) Sulphato
Oxide (O2–) Oxo
Carbonate (CO32–) Carbonato
Oxalate (C2O42–) Oxalato
Thiocyanate (SCN– ) Thiocyanato
Cyanide (CN– ) Cyano
Isothiocyanate (NCS– ) Isothiocyanato
Ethylenediamine (NH2CH2CH2NH2) Etylenediamine
Ammonia (NH3 ) Ammine
Water (H2O) Aqua
Carbon monoxide (CO) Carbonyl
EDTA Ethylenediamineteracetato

4. When several ligands of a particular kind are present, we use the Greek prefix di, tri-
tetra etc to name them. Thus the ligands in cation [Co(NH3)4Cl2]+ are named as
“tetraammine dichloro” (note that prefixes are ignored when alphabetizing ligands).
If the ligand itself contains a Greek prefix, we use the prefixes bis,tris and tetrakis
etc to indicate the number of ligands present. For example, the ligand ethylenediamine
already contains di, therefore, if two such ligands are present the name is
bis(ethylenediamine).
5. The oxidation number of the metal is written in roman numerals following the
name of the metal. For example, the roman numeral III is used to indicate the
+3 oxidation state of chromium in [Cr(NH 3 ) 4 Cl 2 ] + , which is named as
tetraamminedichlorochromium (III) ion.
6. If the complex is an anion, its name ends in –ate. For example, in K 4[Fe(CN)6] the
anion [Fe(CN)6]4– is called hexacyanoferrate(II) ion. Note that the numeral (II) indicate
the oxidation state of iron. Table given below gives tha name of anions containing
metal atoms.
7. If the complex is either a cation or is neutral, no change is required in the name of
the central metal ion. For example [Co(NH 3)6]3+ and [Ni(CO) 4] are named as
hexaamminecobalt(III)ion and tetracarbonyl nickel(0), respectively.
Table 2.4 : Some anions containing metal atoms
Metal Name of metal in anionic state
Copper Cuperate
Zinc Zincate
Aluminum Aluminate
Chromium Chromate
Tin Stannate
Cobalt Cobaltate
Nickel Nickelate
Gold Aurate
Silver Argentate
Lead Plumbate
Rhodium Rhodate
Iron Ferrate
Manganese Manganate
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 Coordination Compounds MODULE - 6
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A. few examples are given below:
[Co(H2O)6]Cl3 hexaaquacobalt(III) chloride
K2[PtCl6] potassium hexachloroplatinate(IV)
[Pt(NH3)2Cl4] diamminetetrachloroplatinum(IV)
[Co(en)2Cl2]Cl dichlorobis (ethylenediamine)cobalt(III) chloride. Notes

Intext Questions 24.3

1. Write down the name of the following complexes:
(a) [Co(NH3)4Cl2]+
(b) (NH4)3[Cr(NCS)6]
(c) Ni(CO)4
(d) K4[Fe(CN)6]
(e) [Cr(en)3]Cl3
................................................................................................................................
2. Write down the formula of the following:
(a) Tetrachloronickelate(II)
(b) Pentaamminenitrocobalt(III) ion
c) Potassium hexacyanoferrate(III)
d) Dichlorobis(ethylenediammine) chromium(III) ion
...............................................................................................................................

24.4 Valence Bond Theory

Linus Pauling of the California Institute of Technology developed the valance bond theory.
He was awarded the Nobel prize in chemistry in 1954. Pauling’s ideas have had an important
impact on all areas of chemistry. He applied valence bond theory to coordination compounds.
This theory can account reasonably well for the structure and magnetic properties of
metal complexes.
The basic principles, which are involved in the valence bond treatment of coordination
compounds are:
(a) Hybridization of valance orbitals of the central metal/ ion
(b) Bonding between ligand and the metal ion/atom.
(c) Relation between the type of bond and the observed magnetic behaviour.
Six Coordinate Complexes
Let us explain by taking simple examples such as [CoF6]3- and [Co(NH3)6]3+. Although in
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 MODULE - 6 Chemistry

Chemistry of Elements both the complexes, the oxidation state of cobalt is +3, but [CoF6]3- is paramagnetic and
[Co(NH3)6]3+ is diamagnetic, why? The formation of a complex may be considered as a
series of hypothetical steps. First the appropriate metal ion is taken e.g. Co3+. Cobalt atom
has the outer electronic configuration 3d74s2. Thus Co3+ ion will have the configuration
3d6 and the electrons will be arranged as:
3d 4s 4p
Notes

+3
Co ion forms both paramagnetic (outer orbital) and diamagnetic (inner orbital)
complexes depending upon the nature of ligands as illustrated below.
As Co3+ ion combines with six fluoride ligands in [CoF6]3–, empty atomic orbitals are
required on the metal ion to receive the coordinated lone pair of electrons. The orbitals
used are one 4s, three 4p and two 4d. These are hybridized to give a set of six equivalent
sp3d2 hybrid orbitals. A ligand orbital containing a lone pair of electron forms a coordinate
bond by overlapping with an empty hybrid orbital on the metal ion. In this way a  bond is
formed with each ligand. The d-orbitals used are the 4d 2 2 and 4d z 2 . It is shown
x y
below:

3d 4s 4p 4d
** ** ** ** ** **
– – –
F F– F– F– F F
sp3d 2, outer orbital complex

Since the outer 4d orbitals are used for bonding, this is called an outer orbital complex. The
energy of these orbitals is quite high, so the complex will be reactive. This complex will be
high-spin paramagnetic, because it has four unpaired electrons.
An alternative octahedral arrangement in [Co(NH3)6]3+ is possible when the electrons on
metal ion are rearranged as shown below:
3d 4s 4p

** ** ** ** ** **

NH3 NH3 NH3 NH3 NH3 NH3

d 2sp3 , inner orbital complex

Since inner d-orbitals are used this is called an inner orbital complex. There is no unpaired
electron, the complex will be low-spin diamagnetic.
The metal ion can also form 4-coordinate complexes. For such complexes two different
arrangements are possible i.e. tetrahedral (sp3) and square planar (dsp2):
3d 4s 4p
** ** ** **
tetrahedral sp3
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 Coordination Compounds MODULE - 6
Chemistry of Elements
3d 4s 4p
** ** **
square planar dsp2

About such complexes you will study later.

Notes
Let us illustrate six coordinate complexes with more examples:
1. Cr(NH3) 6] 3+
The electronic configuration of only 3d, 4s and 4p orbitals are taken into account. The
following steps are involved. The electronic configuration of Cr atom and Cr 3+ ion are
given in (i) and (ii) below:
(i) Cr ground state:

3d 4s 4p

(ii) Cr 3+

3d 4s 4p

(iii) [Cr(NH3)6]3+

3d 4s 4p

** ** ** ** ** **
NH3NH3 NH3 NH3 NH3 NH3
d2sp3 (inner orbital)
The 12 electrons for bond formation come from six ligands, each donating a lone pair of
electrons. The resulting complex will be paramagnetic because it has three unpaired
electrons. Its magnetic moment will be:
n ( n  2)  3( 3  2)  15  3.87B.M
2. [Fe(CN)6]4-
(i) Fe
3d 4s 4p

(ii) Fe 2+
3d 4s 4p

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 MODULE - 6 Chemistry

Chemistry of Elements
(iii) [Fe(CN)6]4–
3d 4s 4p

** ** ** ** ** **
– – –
–
CN CN
–
CN CN– CN CN

Notes d2sp3
The resulting complex is inner orbital, octahedral and due to the absence of unpaired
electron, it will be diamagnetic.
3. [Fe(CN)6]3-
(i) Fe
3d 4s 4p

(ii) Fe 3+
3d 4s 4p

(iii) [Fe(CN)6]3–
3d 4s 4p
** ** ** ** ** **
– – –
– –
CN CN CN CN– CN CN
d 2sp 3
The resulting complex is inner orbital, octahedral. Due to presence of one unpaired electron,
it will be paramagnetic.
Four coordinate complexes:
1. [NiCl4]2-
(i) Ni
3d 4s 4p

(ii) Ni2+
3d 4s 4p

(iii) [NiCl4]2–
3d 4s 4p
** ** ** **
– – –
Cl Cl Cl– Cl

110 sp3
 Coordination Compounds MODULE - 6
Chemistry of Elements
The resulting complex will be tetrahedral with two unpaired electrons. It will be paramagnetic.
2. Ni(CO)4
(i) Ni
3d 4s 4p
Notes
(ii) Ni(O)
3d 4s 4p

(iii) Ni(CO)4

3d 4s 4p
** ** ** **
CO CO CO CO
sp 3
The resulting complex will be tetrahedral. It has no unpaired electrons and will be
diamagnetic.

3. [Ni(CN)4]2-

(i) Ni

3d 4s 4p

(ii) Ni2+

3d 4s 4p

(iii) [Ni(CN)4]2-

3d 4s 4p

** ** ** **
CN –
CN –
CN– CN–

dsp2

The resulting complex is square planar and diamagnetic.

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Intext Questions 24.4
1. Name the type of hybridization present in: [Co(NH3)6]3+..
................................................................................................................................
2. [Fe(CN)6]3– is diamagnetic or paramagnetic?
Notes
................................................................................................................................
3. [NiCl4]2– and Ni(CO)4 have sp3 or dsp2 hybridization?
................................................................................................................................
4. Which one is diamagnetic: [Ni(CN)4]2– or [NiCl4]2–?
................................................................................................................................
5. What type of hybridization is shown by (i) inner and (ii) outer orbital complexes?
................................................................................................................................

24.5 Applications of Coordination Compounds

Coordination compounds are found in living systems and have many uses in the home, in
industry and in medicines. A few examples are given below:
Extraction of metals: cyanide ions are used for the for the extraction of gold and silver.
The crushed ore is heated with an aq. cyanide solution in the presence of air to dissolve the
gold by forming the soluble complex ion [Au(CN)2]–.
4Au(s) + 8CN (aq) + O2(g) + 2H2O(l)  4[Au(CN)2] (aq) + 4 OH (aq)
– – –

Zn(s) + 2[Au(CN)2] (aq)  [Zn(CN)4]2– (aq) + 2Au(s)

–

Complex formation is also useful for the purification of metals. Nickel is purified by
converting the metal to the gaseous compound Ni(CO)4 and then decomposing the latter to
pure nickel.
Medicines: EDTA is a chelating agent which is used in the treatment of lead poisoning.
Cis platin cis [Pt(NH3)2Cl2] is used in the treatment of cancer. Sodium nitroprusside,
Na2[Fe(CN)5NO] is used to lower blood pressure during surgery.
Qualitative Analyses: complex formation is useful for qualitative analyses.
(a) Separation of Ag+ from Pb2+ & Hg2+
Ag+ + 2NH3(aq.)  [Ag(NH3)2]+
Soluble
(b) Separation of IIA and IIB groups: The cations of IIB group form soluble complex
with yellow ammonium sulphide.
(c) Cu2+ ion forms complex on addition of ammonia [Cu(NH3)4]2+.

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 Coordination Compounds MODULE - 6
Chemistry of Elements
(d) Fe2+ forms a blue complex with K3Fe(CN)6, i.e. K FeII[FeIII(CN)6].
(f) Cobalt(II) gives color with HCl due to the formation of complex [CoCl4]2–.
(g) Nickel forms a red complex [Ni(DMG)2] with dimethylglyoxime (H2DMG).

Intext Questions 24.5 Notes

1. Name two elements which are extracted by complexation.
................................................................................................................................
2. What is the use of EDTA in medicine?
................................................................................................................................
3. Name the compound of platinum which is used as anticancer agent?
................................................................................................................................
4. Give two uses of complexes in qualitative analyses
................................................................................................................................

What You Have Learnt

 Coordination compounds are compound in which a central metal ion is attached to a
group of surrounding ligands by coordinate covalent bond. Ligands can be monodentate
or polydentate, depending upon the number of donor atoms attached to the metal.
Polydentate ligands are also called chelating agents. They form complexes that have
rings of atoms known as chelate rings.
 The number of donor atoms bonded to a metal is called the coordination number of
the metal. Common coordination number and geometries are 2 (linear), 4 (tetrahedral
and square planar), and 6 (octahedral).
 Systematic names for complexes specify the number of ligands of each particular
type, the metal, and its oxidation state.
 Valance Bond Theory describes the bonding in complexes in terms of two-electron,
coordinate covalent bonds resulting from the overlap of filled ligand orbitals with
vacant metal hybrid orbitals that point in the direction of the ligands; sp (linear), sp3
(tetrahedral), dsp2 (square planar) and d2sp3 or sp3d2 (octahedral).
 Complexes are very useful in qualitative analyses and in medicine.

Terminal Exercise
1. Define the following:
(i) Coordination number
(ii) Coordination sphere

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 MODULE - 6 Chemistry

Chemistry of Elements
(iii) Oxidation number
2. Define ligands. Give one example of each of monodentate, bidentate and polydentate
ligands.
3. Write the postulates of Werner’s theory of coordination compounds.
4. Write down the name of the following complexes:
Notes
(i) K3[Cr(C 2O4)3]
(ii) [Co(NH3)2(H2O)2Cl2]+
(iii) [Pt(en)2]2+
(iv) [NiCl4]2–
(v) [Fe(CN)6]4–
5. Write down the formulae of the following complexes:
i. Tris(ethylenediamine)platinum(IV)
ii. Tetraaquadibromocobalt(III) ion
iii. Sodium tetraiodozincate(II)
iv. Tetracyanonickelate(II) ion
v. Dichlorotetrathiocyanatochromium(III) ion
6. Give the salient features of VB theory for complexes. What do you mean by inner
and outer orbital complexes?
7. [NiCl4]2– and Ni(CO)4 are tetrahedral but differ in magnetic behaviour, explain.
8. Ni(CO)4 and [Ni(CN)4]2– are diamagnetic but have different geometry, explain.
9. [NiCl4]2– is paramagnetic whereas [Ni(CN)4]2– is diamagnetic, explain.
10. Explain the types of hybridization and magnetic behaviour of the following complexes
on the basis of VB theory:
i. [Fe(CN)6]4–
ii. [Cr(NH3) 6]2+
iii. [Fe(CN)6]3–
iv. [NiCl4]2–
v. Ni(CO)4
11. Explain the application of complexes in extraction of elements, medicines and qualitative
analyses.

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Anwers to Intext Questions

24.1
1. Primary valence corresponds to the oxidation state of the central metal ion. It is
satisfied by negative ions only. Notes
2. Secondary valence of the metal corresponds to coordination number and is satisfied
by negative ions or neutral molecules.
3. In both secondary valance is 6.
4. Octahedral.
5. Two i.e. Tetrahedral or square planar.

24.2
1. (i) 6
(ii) 6
(iii) 4
2. (i) +2
(ii) +3
(iii) +3
(iv) +2
3. EDTA
4. NH3, ethylenediammine and EDTA
5. +3, 6, Ethylenediammine.

24.3
1. (i) Tetraamminedichlorocobalt(III) ion
(ii) Ammonium-hexaisothiocyanatochromate(III)
(iii) Tetracarbonylnickel(0)
(iv) Potassium-hexacyanoferrate(II)
(v) Tris(ethylenediamine)chromium(III) chloride
2. (i) [NiCl4]2–
(ii) [Co(NH3)5NO2]2+
(iii) K3[Fe(CN)6] –
(iv) [Cr(en)2Cl2]+
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Chemistry of Elements
24.4
1. d2sp3
2. [Fe(CN)6]3– is paramagnetic because it has one unpaired electron.
3. Both the complexes have sp3 (tetrahedral) hybridization.
Notes
4. [Ni(CN)4]2– is diamagnetic because it is square planar (dsp2 hybridization). It has no
unpaired electron.
5. Inner – d2sp3, outer – sp3d2

24.5
1. Gold and silver are extracted by cyanide process.
2. EDTA forms soluble complex with elements. It is used in the treatment of lead
poisoning.
3. Cis-platin
4. [Cu(NH3)4]2+ & [Ni(DMG)2]

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 Coordination Compounds
SENIOR SECONDARY COURSEMODULE - 6
Chemistry of Elements
CHEMISTRY
Student’s Assignment – 5

Notes 1
Maximum Marks: 50 Time : 1 Hours
2

INSTRUCTIONS
 Answer all the questions on a separate sheet of paper.
 Give the following information on your answer sheet:
 Name
 Enrolment Number
 Subject
 Assignment Number
 Address
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1. (a) Name the components of Bordeaux mixture.
(b) Define an ore.
(c) How is Flux related to Gangue and Slag?
(d) Define interstial compounds.
(e) Define paramagnetism.
(f) State two uses of sodium bicarbonate.
(g) What are Fullerenes?
(h) Name three isotopes of hydrogen.
(i) Write a chemical reaction showing the strong dehydrating property of sulphuric acid.
(j) Write a chemical reaction showing the formation of nitroglycerine from glycerine.
1 × 10 = 10
2. (a) Name the oxides of phosphorus and draw the structure of anyone of them.
(b) List four characteristics of p-block elements.
(c) Differenciate roasting from calcination.
(d) Defferenciate Electron affinity from Electronegativity.
(e) Despite being in different group lithium shows similarities with Magnesium. Explain.
(f) Hydrated ions of some transition elements appear coloured. Explain.
117
 (g) Elements bearing atomic numbers from 21 to 30 are d-block elements which of them is not a
transition element and why?
(h) List 4 characteristics of Transition Metals.
(i) How is heavy water different from ordinary water?
(j) Draw angular resonance structure of nitric oxide. (2 × 10 = 20)
3. (a) Assign the geometry to the following molecules using the VSEPR theory. State reasons for your
answers.
(i) Phosphorus (V) Chloride (PCl5)
(ii) Sulphur (VI) Flouride (SF6)
(iii) Boron (III) Flouride (BF3).
(b) Potassium permanganate shows different chemical reactions in alkaline, neutral and acidic solutions.
Write one chemical each, showing the difference in behaviour.
(c) How purified Haemetite is converted into iron using the process of smelting. Write the chemical
equations involved.
(d) Write the sequence of chemical reactions involved in the production of washing soda using solvay
process. (3 × 4 = 12)
4. (a) In the table given below the ionization energy (in kJ mol–1) of some elements is shows against their
symbol with atomic number
Li
3 4
Be B
5 6
C 7
N 8
O 9
F 10
Ne
520 900 800 1090 1400 1310 1680 2080

Study the table carefully and explain why the increase in ionization potential is not steady as we
move from left to right.
(b) On the basis of the electronic configuration classify elements bearing atomic number 18, 26, 35
and 27 into the following groups.
(i) Alkaline earth metals
(ii) Noble gases
(iii) Halogens
(iv) Transition elements (4 × 2 = 8)
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Chemistry Notes for class 12 Chapter 9

Coordination Compounds
Coordination compounds are those addition molecular compounds which retain their identity in
solid state as well as in dissolved state. In these compounds. the central metal atom or ion is
linked by ions or molecules with coordinate bonds. e.g., Potassium ferrocyanide, K 4 [Fe(CN)6].

Double Salts

These are the addition molecular compounds which are stable in solid state but dissociate into
constituent ions in the solution. e.g., Mohr’S salt, [FeSO4·(NH4)2SO4 . 6H2O get dissociated
into Fe2+, NH+4 and SO2-4 ions.

Terms Related to Coordination Compounds

1. Complex ion or Coordination Entity

It is an electrically charged species in which central metal atom or ion is surrounded by number
of ions or neutral molecules.

(i) Cationic complex entity It is the complex ion which carries positive charge. e.g.,
[Pt(NH3)4]2+

(ii) Anionic complex entity It is the complex ion which carries negative charge. e.g.,
[Fe(CN)6]4-

2. Central Atom or Ion

The atom or ion to which a fixed number of ions or groups are bound is .ned central atom or
ion. It is also referred as Lewis acid. e.g., in (NiCI2(H2O)4]. Ni is central metal atom. It is
generally transition element or inner-transition element.

3. Ligands

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Ligands is electron donating species (ions or molecules) bound to the Central atom in the
coordination entity.

These may be charged or neutral. LIgands are of the following types :

(i) Unidentate It is a ligand, which has one donor site, i.e., the ligand bound to a metal ion
through a single donor site. e.g., H2O, NH3, etc.

(ii) Didentate It is the ligand. which have two donor sites.

(iii) Polydentate It is the ligand, which have several donor sites. e.g., [EDTA]4- is hexadentate
ligand.

(iv) Ambidentate ligands These are the monodentate ligands which can ligate through two
different sites, e.g., NO-2, SCN-, etc.

(v) Chelating ligands Di or polydentate ligands cause cyclisation around the metal atom which
are known as chelate IS , Such ligands USes two or more donor atoms to bind a single metal
ion and are known as chelating ligands.

More the number of chelate rings, more is the stability of complex.

The stabilisation of coordination compounds due to chelation is known as chelate effect.

π – acid ligands are those ligands which can form π – bond and n-bond by accepting an
appreciable amount of 1t electron density from metal atom to empty π or π – orbitals.

4. Coordination Number

It is defined as the number of coordinate bonds formed by central metal atom, with the ligands.

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e.g., in [PtCI6]2-, Pt has coordination number 6.

In case of monodentate ligands,

Coordination number = number of ligands

In polydentate ligands.

Coordination number = number of ligands * denticity

5. Coordination Sphere

The central ion and the ligands attached to it are enclosed in square bracket which is known as
coordination sphere. The ionisable group written outside the bracket is known as counter ions.

6. Coordination Polyhedron

The spatial arrangement of the ligands which are directly attached to the central atom or ion, is
called coordination polyhedron around the central atom or ion.

7. Oxidation Number of Central Atom

The charge of the complex if all the ligands are removed along with the electron pairs that are
shared with the central atom, is called oxidation number of central atom.

e.g., [CU(CN4)3-, oxidation number of copper is +1, and represented as Cu(I).

Types of Complexes

1. Homoleptic complexes

Complexes in which the metal atom or ion is linked to only one kind of donor atoms, are called
homoleptic complexes e.g., [Co(NH3)6]3+

2. Heteroleptic complexes

Complexes in which the metal atom or ion is linked to more than one kind of donor atoms are
called heteroleptic complexes e.g., [Co(NH3)4CI2]+

3. Labile and Inert complexes

Complexes in which the ligand substitution is fast are known as labile complexes and in which
ligand substitution is slow, are known as inert complexes.

Effective Atomic Number (EAN)

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This concept was proposed by Sidgwick. In a complex, the EAN of metal atom is equal to the
total number of electrons present in it.

EAN = Z – ON of metal + 2 * CN

(where, Z = atomic number of metal atom

ON = oxidation number of metal

and CN = coordination number of complex)

An ion with central metal atom having EAN equal to next inert gas will be more stable.

IUPAC Naming of Complex Compounds

Naming is based on set of rules given by IUPAC.

1. Name of the compound is written in two parts (i) name of cation, and (ii) name of anion.

2. The cation is named first in both positively and negatively charged coordination complexes.

3. The dissimilar ligands are named in au alphabetical order before the name of central metal
atom or ion.
4. For more then one similar ligands. the prefixes di, tri, tetra, etc are added before its name. If
the di, tri, etc already appear in the complex then bis, tris, tetrakis are used.

5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’.

6. Names of the anionic ligands end in ‘0’, names of positive ligands end with ‘ium’ and names
of neutral ligands remains as such. But exception are there as we use aqua for H2O, ammine for
NH3, carbonyl for CO and nitrosyl for NO.

7. Oxidation state for the metal in cation, anion or neutral coordination compounds is indicated
by Roman numeral in parentheses.

8. The name of the complex part is written as one word.

9. If the complex ion is a cation, the metal is named same as the element.

10. The neutral complex molecule is named similar to that of the complex cation.

Some examples are

(i) [Cr(NH3)3(H2O)3]Cl3

triamminetrichlorochromium (III) chloride

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(ii) [Co(H2CH2CH2H2)3]2(SO4)3

tris (ethane-l,2-diamine) cobalt (III) sulphate

(iii) [Ag(NH3)2] [Ag(CN)2]

diamminesilver (I) dicyanoargentate(I)

(iv) K4 [Fe(CN)6]

potassium hexacyanoferrate (II)

Isomerism in Coordination Compounds

Coordination compounds exhibit the following types of isomerism:

1.Structural Isomerism

In this isomerism. isomers have different bonding pattern. Different types of structural isomers
are

(i) Linkage isomerism This type of isomerism is shown by the coordination compounds
having ambidentate ligands. e.g.,

[Co(NH3)5(NO2)]Cl and [Co(NH3)5(ONO)]Cl or pentaammine nitrito- N Cobalt (III) chloride

and pentaammine nitrito-O’Cobalt (III) chloride.

(ii) Coordination isomerism This type of isomerism arises from the interchange of ligands
between cationic and anionic complexes of different metal ions present in a complex, e.g.,

[Cr(NH3)6) [CO(CN)6]and [CO(NH3)6] [Cr(CN)6]

(iii) Ionisation isomerism This isomerism arise due to exchange of ionisable anion with
anionic ligand. e.g..

(iv) Solvate isomerism This is also known as hydrate isomerism. In this isomerism, water is
taken as solvent. It has different number of water molecules in the coordination sphere and
outside it. e.g..

[Co(H2O)6]CI3, [Co(H2O)4C12]Cl·2H2O, [Co(H2O)3Cl3]. 3H2O

2. Stereoisomerism

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Stereoisomers have the same chemical formula and chemical bonds but they have different
spatial arrangement. These are of two types :

(i) Geometrical isomerism Geometrical isomers are of two types i.e., cis and trans isomers.
This isomensm is common in complexes with coordination number 4 and 6.

Geometrical isomerism in complexes with coordination number 4

(i) Tetrahedral complexes do not show geometrical isomerism.

(ii) Square planar complexes of formula [MX2L2] (X and L are unidentate) show geometrical
isomerism. The two X ligands may be arranged adjacent to each other in a cis isomer, or
opposite to each other in a trans isomer, e.g.,

(iii) Square planar complex of the type [MABXL] (where A, B, X, L, are unidentate ligands)
shows three isomers, two cis and one trans.

e.g., [Pt(NH3) (Br)(Cl)(Py)].

Geometrical isomerism in complexes with coordination number 6

Octahedral complexes of formula [MX2L4], in which the two X ligands may be oriented cis or
trans to each other, e.g., [Co(NH3)4Cl2)+.

Octahedral complexes of formula [MX2A2], where X are unidentate ligands and A are bidentate
ligand. form cis and trans isomers, e.g., [CoC12(en)2]’

In octahedral complexes of formula [MA3X3], if three donor atoms of the same ligands occupy
adjacent positions at the corners of an octahedral face. it is known as facial (fae) isomer, when
the positions are around the meridian of the octahedron, it is known as meridional (mer)
isomer. e.g., [Co(NH3)3(NO2)3]

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(ii) Optical isomerism These are the complexes which have chiral structures. It arises when
mirror images cannot be superimposed on one another. These mirror images are called
enantiomers. The two forms are called dextro (d) and laevo (l) forms.

Tetrahedral complexes with formula [M(AB)2] show optical isomers and octahedral complexes
(cis form) exhibit optical isomerism.

Bonding in Coordination Compounds

Werner’s Theory

Metals exhibit two types of valencies in the formation of complexes.

These are primary valencies and secondary valencies.

1. Primary valencies correspond to oxidation number (ON) of the metal and are satisfied by
anions. These are ionisable and non-directional.

2. Secondary valencies correspond to coordination number (CN) of the metal atom and are
satisfied by ligands. These are non-ionisable and directional. Hence, geometry is decided by
these valencies.

Valence Bond Theory (VBT)

This theory was proposed by L. Pauling in 1930 s. According to this theory, when a complex is
formed, the metal ion/atom provides empty orbitals to the surrounding ligands. Coordination
number shows the number of such empty orbitals, i.e., number of empty orbitals is equal to the
coordination number. These empty orbitals hybridised
before participation in bonding and the nature of hybridisation depends on the nature of metal
and on the nature of approaching ligand.

Inner orbital complexes or outer orbital complexes

When outer d-orbital are used in bonding, the complexes are called outer orbital complexes.
They are formed due to weak field ligands or high spin ligands and hybridisation is sp3d2. They
have octahedral shape.

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When d-orbitals of (n – 1) shell are used, these are known as inner orbital complex, they are
formed due to strong field ligands or low spin ligands and hybridisation is d 2sp3. They are also
octahedral in shape.

1. 6 – ligands (unidentate), octahedral entity.

(i) Inner orbital complex [Co(NH3)6]3+

All electrons are paired, therefore complex will be diamagnetic in nature.

(ii) Outer orbital complex, [CoF6]3-

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Complex has unpaired electrons, therefore, it will be paramagnetic in nature.

2. 4-ligands (unidentate) tetrahedral entity.

(i) Inner orbital complex, [Ni(CN)4]2-

All electrons are paired so complex will be diamagnetic in nature.

(ii) Outer orbital complex, [CoCI4]-

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Since, complex has unpaired electrons. so it will be paramagnetic in nature.

Limitations of VBT

This theory could not explain the quantisation of the magnetic data, existence of inner orbital
and outer orbital complex, change of magnetic moment with temperature and colour of
complexes.

Crystal Field Theory (eFT)

This theory was proposed by H. Bethe and van Vleck. Orgel. in 1952, applied this theory to
coordination compounds. In this theory, ligands are treated as point charges in case of anions
and dipoles in case of neutral molecules.

The five d-orbitals are classified as

(i) Three d-orbitals i.e., dxy, dyz and dzx are oriented in between the coordinate axes and are
called t2g – orbitals.

(ii) The other two d-orbitals, i.e., d x2 - y2 and d z2 oriented along the x – y % axes are called eg –
orbitals.

Due to approach of ligands, the five degenerate d-orbitals split. Splitting of d-orbitals depends
on the nature of the crystal field.

[The energy difference between t2g and eg level is designated by Δ and is called crystal field
splitting energy.]

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By using spectroscopic data for a number of coordination compounds, having the same metal
ions but different ligand, the crystal field splitting for each ligand has been calculated. A series
in which ligand are arranged in order of increasing magnitude of crystal field splitting, is
called spectrochemical series.

Spectrochemical series

Crystal field splitting in octahedral complexes

In case of octahedral complexes, energy separation is denoted by Δo (where subscript 0 is for

octahedral).

In octahedral complexes, the six-ligands approach the central metal ion along the axis of d x2 -
2 2
y and d z orbitals.

Energy of eg set of orbitals > energy of t2g set of orbitals.

The energy of eg orbitals will increase by (3/5) Δo and t2g will decrease by (2/5) Δo.

If Δo < P, the fourth electron enters one of the eg orbitals giving the configuration t32g e1g.
Ligands for which Δo < P are known as weak field ligands and form high spin complexes.

If Δo > P, it becomes more energetically favourable for the fourth electron to occupy a
t2g orbital with configuration t42g eog. (where, P = energy required for e- pairing in an orbital).
Ligands which produce this effect are known as strong field ligands and form low spin
complexes.

Crystal field splitting in tetrahedral complexes

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In tetrahedral complexes, four ligands may be imagined to occupy the alternate comers of the
cube and the metal ion at the center of the cube.

Energy of t2g set of orbitals > Energy of eg set of orbitals.

In such complexes d – orbital splitting is inverted and is smaller as compared to the octahedral
field splitting.

Orbital splitting energies are so low that pairing of electrons are not possible so these are high
spin complexes.

Colour in Coordination Compounds

The crystal field theory attributes the colour of the coordination compounds to dod transition of
the electron, i.e., electron jump from t2g level to higher eg level.

In the absence of ligands, crystal field splitting does not occur and hence the substance is
colourless.

Limitations of CFT

1. It does not consider the formation of 7t bonding in complexes.

2. It is also unable to account satisfactorily for the relative strengths of ligands e.g., it does not
explain why H2O is stronger ligand than OH-.
3. It gives no account of the partly covalent nature of metal-metal bonds.

Ligand Field or Molecular Orbital Theory

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This theory was put forward by Hund and Mulliken. According to this theory, all the atomic
orbitals of the atom participating in molecule formation get mixed to give rise an equivalent
number of new orbitals, called the molecular orbitals. The electrons are now under the
influence of all the nuclei.

Stability of Coordination Compounds

The stability of complex in solution refers to the degree of association between the two species
involved in the state of equilibrium. It is expressed as stability constant (K).

The factors on which stability of the complex depends :

(i) Charge on the central metal atom As the magnitude of charge on metal atom increases,
stability of the complex increases.
(ii) Nature of metal ion The stability order is 3d < 4d < 5d series.
(iii) Basic nature of ligands Strong field ligands form stable complex.

The instability constant or the dissociation constant of compounds is defined as the reciprocal
of the formation or stability Constant.

Importance and Applications of Coordination Compounds

1. They are used in many qualitative and quantitative analysis.

2. Hardness of water is estimated by simple titration with Na2 EDTA.
3. Purification of metals can be achieved through formation and subsequent decomposition of
their coordination compounds.
4. They have great importance in biological systems.
5. They are used as catalyst for many industrial processes.
6. In medicinal chemistry, there is a growing interest of chelating therapy.

Organometallic Compounds

They contain one or more metal-carbon bond in their molecules. They are of the following
types:

1. Sigma (σ) bonded compounds

Metal-carbon bond is sigma bond, e.g., (C2H5)4 Pb, Zn(C2H5)2 R – Mg – X, etc.

2. Pi(π) bonded compounds

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In which molecules/ions containing π bonds act as a ligand. e.g., Ferrocene, Dibenzene

chromium and Zeise’s salt.

Zeise’s salts is K[PtCI3(η2 – C2H4)] In which ethylene acts as a ligand which do not have a lone
pair oi electron.

In ferrocene, Fe(η5 – C5H5)2 represents the number of carbon atoms with which metal ion is
directly attached.

3. σ and π bonded compounds

Metal carbonyls are their examples. Metal-carbon bond of metal carbonyls have both σ and π –
bond character. They have CO molecule as ligand, e.g.,

Wilkinson’s catalyst (Rh(PPh3)3CI] is used as homogeneous catalyst in the hydrogenation of

alkenes. Zeigler-Natta catalyst
[Ti CI4 + (C2H5>3Al] acts as heterogeneous catalyst in the polymerisation of ethylene

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Chemistry Notes for class 12 Chapter 9

Coordination Compounds
Coordination compounds are those addition molecular compounds which retain their identity in
solid state as well as in dissolved state. In these compounds. the central metal atom or ion is
linked by ions or molecules with coordinate bonds. e.g., Potassium ferrocyanide, K 4 [Fe(CN)6].

Double Salts

These are the addition molecular compounds which are stable in solid state but dissociate into
constituent ions in the solution. e.g., Mohr’S salt, [FeSO4·(NH4)2SO4 . 6H2O get dissociated
into Fe2+, NH+4 and SO2-4 ions.

Terms Related to Coordination Compounds

1. Complex ion or Coordination Entity

It is an electrically charged species in which central metal atom or ion is surrounded by number
of ions or neutral molecules.

(i) Cationic complex entity It is the complex ion which carries positive charge. e.g.,
[Pt(NH3)4]2+

(ii) Anionic complex entity It is the complex ion which carries negative charge. e.g.,
[Fe(CN)6]4-

2. Central Atom or Ion

The atom or ion to which a fixed number of ions or groups are bound is .ned central atom or
ion. It is also referred as Lewis acid. e.g., in (NiCI2(H2O)4]. Ni is central metal atom. It is
generally transition element or inner-transition element.

3. Ligands

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Ligands is electron donating species (ions or molecules) bound to the Central atom in the
coordination entity.

These may be charged or neutral. LIgands are of the following types :

(i) Unidentate It is a ligand, which has one donor site, i.e., the ligand bound to a metal ion
through a single donor site. e.g., H2O, NH3, etc.

(ii) Didentate It is the ligand. which have two donor sites.

(iii) Polydentate It is the ligand, which have several donor sites. e.g., [EDTA]4- is hexadentate
ligand.

(iv) Ambidentate ligands These are the monodentate ligands which can ligate through two
different sites, e.g., NO-2, SCN-, etc.

(v) Chelating ligands Di or polydentate ligands cause cyclisation around the metal atom which
are known as chelate IS , Such ligands USes two or more donor atoms to bind a single metal
ion and are known as chelating ligands.

More the number of chelate rings, more is the stability of complex.

The stabilisation of coordination compounds due to chelation is known as chelate effect.

π – acid ligands are those ligands which can form π – bond and n-bond by accepting an
appreciable amount of 1t electron density from metal atom to empty π or π – orbitals.

4. Coordination Number

It is defined as the number of coordinate bonds formed by central metal atom, with the ligands.

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e.g., in [PtCI6]2-, Pt has coordination number 6.

In case of monodentate ligands,

Coordination number = number of ligands

In polydentate ligands.

Coordination number = number of ligands * denticity

5. Coordination Sphere

The central ion and the ligands attached to it are enclosed in square bracket which is known as
coordination sphere. The ionisable group written outside the bracket is known as counter ions.

6. Coordination Polyhedron

The spatial arrangement of the ligands which are directly attached to the central atom or ion, is
called coordination polyhedron around the central atom or ion.

7. Oxidation Number of Central Atom

The charge of the complex if all the ligands are removed along with the electron pairs that are
shared with the central atom, is called oxidation number of central atom.

e.g., [CU(CN4)3-, oxidation number of copper is +1, and represented as Cu(I).

Types of Complexes

1. Homoleptic complexes

Complexes in which the metal atom or ion is linked to only one kind of donor atoms, are called
homoleptic complexes e.g., [Co(NH3)6]3+

2. Heteroleptic complexes

Complexes in which the metal atom or ion is linked to more than one kind of donor atoms are
called heteroleptic complexes e.g., [Co(NH3)4CI2]+

3. Labile and Inert complexes

Complexes in which the ligand substitution is fast are known as labile complexes and in which
ligand substitution is slow, are known as inert complexes.

Effective Atomic Number (EAN)

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This concept was proposed by Sidgwick. In a complex, the EAN of metal atom is equal to the
total number of electrons present in it.

EAN = Z – ON of metal + 2 * CN

(where, Z = atomic number of metal atom

ON = oxidation number of metal

and CN = coordination number of complex)

An ion with central metal atom having EAN equal to next inert gas will be more stable.

IUPAC Naming of Complex Compounds

Naming is based on set of rules given by IUPAC.

1. Name of the compound is written in two parts (i) name of cation, and (ii) name of anion.

2. The cation is named first in both positively and negatively charged coordination complexes.

3. The dissimilar ligands are named in au alphabetical order before the name of central metal
atom or ion.
4. For more then one similar ligands. the prefixes di, tri, tetra, etc are added before its name. If
the di, tri, etc already appear in the complex then bis, tris, tetrakis are used.

5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’.

6. Names of the anionic ligands end in ‘0’, names of positive ligands end with ‘ium’ and names
of neutral ligands remains as such. But exception are there as we use aqua for H2O, ammine for
NH3, carbonyl for CO and nitrosyl for NO.

7. Oxidation state for the metal in cation, anion or neutral coordination compounds is indicated
by Roman numeral in parentheses.

8. The name of the complex part is written as one word.

9. If the complex ion is a cation, the metal is named same as the element.

10. The neutral complex molecule is named similar to that of the complex cation.

Some examples are

(i) [Cr(NH3)3(H2O)3]Cl3

triamminetrichlorochromium (III) chloride

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(ii) [Co(H2CH2CH2H2)3]2(SO4)3

tris (ethane-l,2-diamine) cobalt (III) sulphate

(iii) [Ag(NH3)2] [Ag(CN)2]

diamminesilver (I) dicyanoargentate(I)

(iv) K4 [Fe(CN)6]

potassium hexacyanoferrate (II)

Isomerism in Coordination Compounds

Coordination compounds exhibit the following types of isomerism:

1.Structural Isomerism

In this isomerism. isomers have different bonding pattern. Different types of structural isomers
are

(i) Linkage isomerism This type of isomerism is shown by the coordination compounds
having ambidentate ligands. e.g.,

[Co(NH3)5(NO2)]Cl and [Co(NH3)5(ONO)]Cl or pentaammine nitrito- N Cobalt (III) chloride

and pentaammine nitrito-O’Cobalt (III) chloride.

(ii) Coordination isomerism This type of isomerism arises from the interchange of ligands
between cationic and anionic complexes of different metal ions present in a complex, e.g.,

[Cr(NH3)6) [CO(CN)6]and [CO(NH3)6] [Cr(CN)6]

(iii) Ionisation isomerism This isomerism arise due to exchange of ionisable anion with
anionic ligand. e.g..

(iv) Solvate isomerism This is also known as hydrate isomerism. In this isomerism, water is
taken as solvent. It has different number of water molecules in the coordination sphere and
outside it. e.g..

[Co(H2O)6]CI3, [Co(H2O)4C12]Cl·2H2O, [Co(H2O)3Cl3]. 3H2O

2. Stereoisomerism

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Stereoisomers have the same chemical formula and chemical bonds but they have different
spatial arrangement. These are of two types :

(i) Geometrical isomerism Geometrical isomers are of two types i.e., cis and trans isomers.
This isomensm is common in complexes with coordination number 4 and 6.

Geometrical isomerism in complexes with coordination number 4

(i) Tetrahedral complexes do not show geometrical isomerism.

(ii) Square planar complexes of formula [MX2L2] (X and L are unidentate) show geometrical
isomerism. The two X ligands may be arranged adjacent to each other in a cis isomer, or
opposite to each other in a trans isomer, e.g.,

(iii) Square planar complex of the type [MABXL] (where A, B, X, L, are unidentate ligands)
shows three isomers, two cis and one trans.

e.g., [Pt(NH3) (Br)(Cl)(Py)].

Geometrical isomerism in complexes with coordination number 6

Octahedral complexes of formula [MX2L4], in which the two X ligands may be oriented cis or
trans to each other, e.g., [Co(NH3)4Cl2)+.

Octahedral complexes of formula [MX2A2], where X are unidentate ligands and A are bidentate
ligand. form cis and trans isomers, e.g., [CoC12(en)2]’

In octahedral complexes of formula [MA3X3], if three donor atoms of the same ligands occupy
adjacent positions at the corners of an octahedral face. it is known as facial (fae) isomer, when
the positions are around the meridian of the octahedron, it is known as meridional (mer)
isomer. e.g., [Co(NH3)3(NO2)3]

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(ii) Optical isomerism These are the complexes which have chiral structures. It arises when
mirror images cannot be superimposed on one another. These mirror images are called
enantiomers. The two forms are called dextro (d) and laevo (l) forms.

Tetrahedral complexes with formula [M(AB)2] show optical isomers and octahedral complexes
(cis form) exhibit optical isomerism.

Bonding in Coordination Compounds

Werner’s Theory

Metals exhibit two types of valencies in the formation of complexes.

These are primary valencies and secondary valencies.

1. Primary valencies correspond to oxidation number (ON) of the metal and are satisfied by
anions. These are ionisable and non-directional.

2. Secondary valencies correspond to coordination number (CN) of the metal atom and are
satisfied by ligands. These are non-ionisable and directional. Hence, geometry is decided by
these valencies.

Valence Bond Theory (VBT)

This theory was proposed by L. Pauling in 1930 s. According to this theory, when a complex is
formed, the metal ion/atom provides empty orbitals to the surrounding ligands. Coordination
number shows the number of such empty orbitals, i.e., number of empty orbitals is equal to the
coordination number. These empty orbitals hybridised
before participation in bonding and the nature of hybridisation depends on the nature of metal
and on the nature of approaching ligand.

Inner orbital complexes or outer orbital complexes

When outer d-orbital are used in bonding, the complexes are called outer orbital complexes.
They are formed due to weak field ligands or high spin ligands and hybridisation is sp3d2. They
have octahedral shape.

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When d-orbitals of (n – 1) shell are used, these are known as inner orbital complex, they are
formed due to strong field ligands or low spin ligands and hybridisation is d 2sp3. They are also
octahedral in shape.

1. 6 – ligands (unidentate), octahedral entity.

(i) Inner orbital complex [Co(NH3)6]3+

All electrons are paired, therefore complex will be diamagnetic in nature.

(ii) Outer orbital complex, [CoF6]3-

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Complex has unpaired electrons, therefore, it will be paramagnetic in nature.

2. 4-ligands (unidentate) tetrahedral entity.

(i) Inner orbital complex, [Ni(CN)4]2-

All electrons are paired so complex will be diamagnetic in nature.

(ii) Outer orbital complex, [CoCI4]-

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Since, complex has unpaired electrons. so it will be paramagnetic in nature.

Limitations of VBT

This theory could not explain the quantisation of the magnetic data, existence of inner orbital
and outer orbital complex, change of magnetic moment with temperature and colour of
complexes.

Crystal Field Theory (eFT)

This theory was proposed by H. Bethe and van Vleck. Orgel. in 1952, applied this theory to
coordination compounds. In this theory, ligands are treated as point charges in case of anions
and dipoles in case of neutral molecules.

The five d-orbitals are classified as

(i) Three d-orbitals i.e., dxy, dyz and dzx are oriented in between the coordinate axes and are
called t2g – orbitals.

(ii) The other two d-orbitals, i.e., d x2 - y2 and d z2 oriented along the x – y % axes are called eg –
orbitals.

Due to approach of ligands, the five degenerate d-orbitals split. Splitting of d-orbitals depends
on the nature of the crystal field.

[The energy difference between t2g and eg level is designated by Δ and is called crystal field
splitting energy.]

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By using spectroscopic data for a number of coordination compounds, having the same metal
ions but different ligand, the crystal field splitting for each ligand has been calculated. A series
in which ligand are arranged in order of increasing magnitude of crystal field splitting, is
called spectrochemical series.

Spectrochemical series

Crystal field splitting in octahedral complexes

In case of octahedral complexes, energy separation is denoted by Δo (where subscript 0 is for

octahedral).

In octahedral complexes, the six-ligands approach the central metal ion along the axis of d x2 -
2 2
y and d z orbitals.

Energy of eg set of orbitals > energy of t2g set of orbitals.

The energy of eg orbitals will increase by (3/5) Δo and t2g will decrease by (2/5) Δo.

If Δo < P, the fourth electron enters one of the eg orbitals giving the configuration t32g e1g.
Ligands for which Δo < P are known as weak field ligands and form high spin complexes.

If Δo > P, it becomes more energetically favourable for the fourth electron to occupy a
t2g orbital with configuration t42g eog. (where, P = energy required for e- pairing in an orbital).
Ligands which produce this effect are known as strong field ligands and form low spin
complexes.

Crystal field splitting in tetrahedral complexes

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In tetrahedral complexes, four ligands may be imagined to occupy the alternate comers of the
cube and the metal ion at the center of the cube.

Energy of t2g set of orbitals > Energy of eg set of orbitals.

In such complexes d – orbital splitting is inverted and is smaller as compared to the octahedral
field splitting.

Orbital splitting energies are so low that pairing of electrons are not possible so these are high
spin complexes.

Colour in Coordination Compounds

The crystal field theory attributes the colour of the coordination compounds to dod transition of
the electron, i.e., electron jump from t2g level to higher eg level.

In the absence of ligands, crystal field splitting does not occur and hence the substance is
colourless.

Limitations of CFT

1. It does not consider the formation of 7t bonding in complexes.

2. It is also unable to account satisfactorily for the relative strengths of ligands e.g., it does not
explain why H2O is stronger ligand than OH-.
3. It gives no account of the partly covalent nature of metal-metal bonds.

Ligand Field or Molecular Orbital Theory

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This theory was put forward by Hund and Mulliken. According to this theory, all the atomic
orbitals of the atom participating in molecule formation get mixed to give rise an equivalent
number of new orbitals, called the molecular orbitals. The electrons are now under the
influence of all the nuclei.

Stability of Coordination Compounds

The stability of complex in solution refers to the degree of association between the two species
involved in the state of equilibrium. It is expressed as stability constant (K).

The factors on which stability of the complex depends :

(i) Charge on the central metal atom As the magnitude of charge on metal atom increases,
stability of the complex increases.
(ii) Nature of metal ion The stability order is 3d < 4d < 5d series.
(iii) Basic nature of ligands Strong field ligands form stable complex.

The instability constant or the dissociation constant of compounds is defined as the reciprocal
of the formation or stability Constant.

Importance and Applications of Coordination Compounds

1. They are used in many qualitative and quantitative analysis.

2. Hardness of water is estimated by simple titration with Na2 EDTA.
3. Purification of metals can be achieved through formation and subsequent decomposition of
their coordination compounds.
4. They have great importance in biological systems.
5. They are used as catalyst for many industrial processes.
6. In medicinal chemistry, there is a growing interest of chelating therapy.

Organometallic Compounds

They contain one or more metal-carbon bond in their molecules. They are of the following
types:

1. Sigma (σ) bonded compounds

Metal-carbon bond is sigma bond, e.g., (C2H5)4 Pb, Zn(C2H5)2 R – Mg – X, etc.

2. Pi(π) bonded compounds

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In which molecules/ions containing π bonds act as a ligand. e.g., Ferrocene, Dibenzene

chromium and Zeise’s salt.

Zeise’s salts is K[PtCI3(η2 – C2H4)] In which ethylene acts as a ligand which do not have a lone
pair oi electron.

In ferrocene, Fe(η5 – C5H5)2 represents the number of carbon atoms with which metal ion is
directly attached.

3. σ and π bonded compounds

Metal carbonyls are their examples. Metal-carbon bond of metal carbonyls have both σ and π –
bond character. They have CO molecule as ligand, e.g.,

Wilkinson’s catalyst (Rh(PPh3)3CI] is used as homogeneous catalyst in the hydrogenation of

alkenes. Zeigler-Natta catalyst
[Ti CI4 + (C2H5>3Al] acts as heterogeneous catalyst in the polymerisation of ethylene

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4.1.2: Introduction to Ligand Field Theory (Octahedral complexes)
Concepts from molecular orbital theory are useful in understanding the reactivity of coordination compounds. One of the basic
ways of applying MO concepts to coordination chemistry is in Ligand Field Theory. Ligand Field Theory looks at the effect of
donor atoms on the energy of d orbitals in the metal complex.
There are two ways in which we sometimes think about the effect of ligands on the d electrons on a metal. On the basis of simple
electron-electron repulsion, donation of a lone pair might raise an occupied d orbital in energy. Alternatively, we can think about
bonding interactions between ligand orbitals and d orbitals. This second way of thinking about things is a little bit more useful, and
that's the approach we'll focus on here.
Either way, there are interactions between ligand electrons and d electrons that usually end up raising the energy of the d electrons.
The effect depends on the coordination geometry of the ligands. Ligands in a tetrahedral coordination sphere will have a different
effect than ligands in an octahedral coordination sphere because they will interact with the different d orbitals in different ways.

Ligand Field Theory looks at the effect of donor atoms on the energy of d orbitals in the
metal complex.
The effect depends on the coordination geometry geometry of the ligands.

Octahedral case
Suppose a complex has an octahedral coordination sphere. Assume the six ligands all lie along the x, y and z axes.

Figure 4.1.2.1 :
There are two d orbitals that will interact very strongly with these ligands: the dx2-y2, which lies directly on the x and y axes, and
the dz2, which lies directly on the z axis. Together, these two metal orbitals and the ligand orbitals that interact with them will form
new bonding and antibonding molecular orbitals.

Figure 4.1.2.2 :
The drawing below is simplified. The ligands will also interact with s and p orbitals, but for the moment we're not going to worry
about them. We also won't worry about interactions from the other four ligands with the d orbitals (possible by symmetry
considerations, but also a more complicated picture).

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 Figure 4.1.2.3 : Diagram of d orbitals (left) and ligands (L1 and L2 on the right) along with their corresponding energy. The orbitals
in the middle represent the bonding combination. Energy increases from bottom to top.
Now, remember that metals usually have d electrons that are much higher in energy than those on typical donor atoms (like oxygen,
sulfur, nitrogen or phosphorus). That means the antibonding combinations will be much closer in energy to the original d orbitals,
because both are relatively high in energy. The bonding combination will be much closer in energy to the original ligand orbitals,
because these ones are all relatively low in energy.
That energetic similarity generally translates into a similarity in shape and location as well. In other words, the antibonding
combination between a d orbital and a ligand orbital is a lot like the original d orbital. The bonding combination is more like the
original ligand orbital than the original d orbital. Because of those similarities, inorganic chemists often refer to those antibonding
orbitals as if they were still the original d orbitals.
These two orbitals will be raised relatively high in energy by sigma bonding interactions with the donor orbitals. If there are
electrons in the picture, it might look something like this:

Figure 4.1.2.4 :
Assume the six ligands all lie along the x, y and z axes.
The dx2-y2 and the dz2 orbitals lie along the bond axes.
These two orbitals will be raised relatively high in energy.
These orbitals are like antibonding levels.
These orbitals are sometimes called the "eg" set of orbitals. The term "eg" comes from the mathematics of symmetry.

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On the other hand, the other three d orbitals, the dxy, dxz and dyz, all lie between the donor ligands, rather than hitting them head-on.
These orbitals will interact less strongly with the donor electrons.
The dxy, dxz and dyz orbitals all lie between the bond axes.
These three orbitals will be changed in energy only a little.
These orbitals are more like non-bonding orbitals.
These orbitals are sometimes called the "t2g" set of orbitals.
Remember, only the energy of the electrons affects the overall energy of the system. The unoccupied d orbitals are raised in energy,
but the occupied orbitals go down in energy (or else stay the same).
Apart from the stabilization of the complex, there is another consequence of this picture. What we are left with is two distinct sets
of d energy levels, one lower than the other. That will have an effect on the electron configuration at the metal atom in the complex.
In other words, there will be cases where electrons could be paired or unpaired, depending on how these orbitals are occupied.
Take the case of the biologically important iron(II) ion. It has a d6 valence electron configuration. In less formal parlance of
inorganic chemistry, "iron(II) is d6." In an iron(II) ion all alone in space, all the d orbitals would have the same energy level. We
would put one electron in each orbital, and have one left. The left over electron would need to pair up in one of the d orbitals
(Notice that, in the chemistry of transition metal ions, the valence s and p orbitals are always assumed to be unoccupied).

Figure 4.1.2.5 :
Things are very different in an octahedral complex, like K4[Fe(CN)6]. In that case, the d orbitals are no longer at the same energy
level. There are two possible configurations to consider.
In one case, one electron would go into each of the lower energy d orbitals. A choice would be made for the fourth electron. Does it
go into the higher energy d orbital, or does it pair up with one of the lower energy d electrons? The choice depends on how much
higher in energy the upper d orbitals are, compared to how much energy it costs to put two electrons in the same d orbital.

Figure 4.1.2.6 :
If the "d orbital splitting energy" is pretty low, so that the two sets of d orbitals are still pretty similar in energy, the next electron
can go into a higher orbital. Pairing would not be required until the final electron. Overall, that would leave four unpaired electrons,
just like in the case of a lone metal ion in space. This is called the "high-spin" case, because electrons can easily go into the higher
orbital.

Figure 4.1.2.7 :
If the d orbital splitting energy is too high, the next electron must pair up in a lower orbital. All three remaining electrons pair up,
and so there are no unpaired electrons in the complex. This is called the "low-spin" case, because electrons more easily pair up in
the orbital.
So the overall rule is that if the energy to pair up the electrons is greater than the energy needed to get to the next level, the electron
will go ahead and occupy the next level.

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 Figure 4.1.2.8 :
However, if the energy it takes to get to the next level is more than it would cost to pair up, the electrons will just pair up instead.

Figure 4.1.2.9 :

The electron configuration can be "high spin" or "low-spin", depending on how large the
energy splitting is between the two sets of d orbitals.
The difference between the high-spin case and the low-spin case is significant because unpaired electrons affect the magnetic
properties of a material. The low-spin case would be diamagnetic, resulting in no interaction with a magnetic field. However, the
high-spin case would be paramagnetic, and would be attracted to a magnetic field.
It turns out K4[Fe(CN)6] is diamagnetic. Thus, it is pretty clear that it is a low-spin complex. The energy difference between the
two d orbital levels is relatively large in this case.
In addition to influencing magnetic properties, whether a complex is high- or low-spin also influences reactivity. Compounds with
high-energy d electrons are generally more labile, meaning they let go of ligands more easily.
electron configuration influences magnetic properties
electron configuration influences lability (how easily ligands are released)

Reasons for Low-spin vs. High-spin: The Effect of the Metal Ion
There are a few factors that determine the magnitude of the d orbital splitting and dictate whether or not an electron can occupy the
higher energy set of orbitals instead of pairing up. These factors are based partly on ligand field strength, which is explored on the
next page. They also depend on the charge on the metal ion and whether the metal is in the first, second, or third row of the
transition metals.
The higher the charge on the metal, the greater the splitting between the d orbital energy levels. For example, Fe(II) is usually high
spin. It has a smaller splitting between the lower and higher d orbital levels, so electrons can more easily go to the higher level
rather than pair up un the lower level.
On the other hand, Fe(III) is usually low spin. It has a larger splitting between the d levels. In that case, it costs less energy for
electrons to pair up in the lower level than to go up to the higher level.
High-spin versus low-spin cases involve a trade-off between the d orbital splitting energy and the pairing energy.

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 2nd and 3rd row transition metals are usually low spin
1st row transition metals are often high spin
However, 1st row transition metals and be low spin if they are very positive (usually 3+ or greater)
There is a lot going on in metal ions, but we'll take a simplified view of things. Thinking only about electrostatics, we can try to
imagine what happens to those electrons when the charge on the metal ion changes.
First we need to know about Coulomb's law. Coulomb's law states that the force of attraction between the electron and the nucleus
depends on only two factors: the amount of positive charge in the nucleus, and the distance between the nucleus and the electron.
The greater the charge on the nucleus, the greater the attraction between the electron and the nucleus.

Figure 4.1.2.10 :
The farther an electron is from the nucleus, the weaker the attraction between the electron and the nucleus.

Figure 4.1.2.11 :
Coulomb's law can be used to evaluate the potential energy of the electron. It is one of the factors that determines how high or low
those electronic energy levels are that we see in energy level diagrams for atoms, ions and molecules. The energy of the electron
varies in a roughly similar way: the greater the charge on the nucleus, the lower the energy of the electron. Also, the closer the
electron is to the nucleus, the lower its energy.

Figure 4.1.2.12 :
Roughly speaking, electrons at higher energy are farther from the nucleus. Electrons at lower energy are closer to the nucleus.
What happens if the charge increases? Maybe a lot more protons are added to the nucleus. Maybe some electrons are lost, so that to
the remaining electrons it just feels like the charge of the nucleus has increased. Then the electrons should be more attracted to the

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nucleus. They get a little closer. Their potential energy drops.

Figure 4.1.2.13 :

Of course, if one electron is closer to the nucleus already, it feels that increase in positive charge more strongly than an electron that
is farther away. Consequently it drops further in energy than an electron that is further away.
If we translate that idea into a picture of the d orbital energy levels in an octahedral geometry, it looks like this:

Figure 4.1.2.14 :
When the charge on the metal ion is increased, both the higher and the lower levels drop in energy. However, the lower level drops
more. Thus, the gap between the levels gets wider.
Metals in the second and third row of the periodic table almost never form high-spin complexes. The d orbital energy splitting in
these cases is larger than for first row metals. From a very simple point of view, these metals have many more protons in their
nuclei than the first row transition metals, dropping that lower set of d electrons lower with respect to the higher set.
That isn't the whole picture for the second and third row transition metals, however. Remember, we are simplifying, and there are
factors we won't go into. However, it is important to know that metal-ligand bond strengths are much greater in the second and
third row than in the first. We'll look at the whole interaction diagram for an octahedral complex now, including contributions form
metal s and p orbitals.

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 Figure 4.1.2.15 :
Like all ligand-metal interaction diagrams, the energy levels of the ligands by themselves are shown on one side. The metal's
electronic energy levels are shown on the other side. The result of their interaction, a metal-ligand complex, is shown in the middle.
The d orbital splitting diagram is shown in a box.
Suppose the diagram above is for a first row transition metal. The diagram for a second or third row metal is similar, but with
stronger bonds.

Figure 4.1.2.16 :
If the bonding interaction is stronger between the metal and ligand, then so is the antibonding interaction. The antibonding levels
are bumped higher in energy as the bonding levels sink lower. Generally that's OK, because when the electrons are filled in, they
will be found preferentially at the lower levels, not the higher ones. There will be a net lowering of electronic energy.
Why do second and third row transition metals form such strong bonds? Bond strengths are very complicated. In general, there is
greater covalency between these metals and their ligands because of increased spatial and energetic overlap. Rather than go into
those factors, we'll just think about all those extra protons in the nucleus that are attracting the ligand electrons more strongly.

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There is one more important distinction that makes second and third row transition metals low spin. In addition, the pairing energy
is lower in these metals because the orbitals are larger. There is more room for two electrons in one orbital, with less repulsion. As
a result, electrons are much more likely to pair up than to occupy the next energy level.
2nd and 3rd row transition metals have stronger bonds, leading to a larger gap between d orbital levels
2nd and 3rd row transition metals have more diffuse orbitals, leading to a lower pairing
energy
It is significant that most important transition metal ions in biology are from the first row of the transition block and are pretty
labile. That fact plays an important role in the ease of formation and deconstruction of transition-metal containing proteins. In
terms of formation, if the metal is more easily released by its previous ligands (either water or some compound that delivers the
metal to the site of protein construction), it can form the necessary protein more quickly. However, even if a metal-containing
enzyme plays a useful role, it should not be too stable, because we need to be able to regulate the level of protein concentration for
optimum activity, or disassemble protein if it becomes damaged. Thus, it is important that the metal ion can be removed easily.

 Exercise 4.1.2.1
Draw both high spin and low spin d-orbital splitting diagrams for the following ions in an octahedral environment and
determine the number of unpaired electrons in each case.
a) Mn2+ b) Co2+ c) Ni2+ d) Cu+ e) Fe3+ f) Cr2+ g) Zn2+

Answer a)

Answer b)

Answer c)

Answer d)

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Answer e)

Answer f)

Answer g)

 Exercise 4.1.2.2

The d orbital splitting diagram for a tetrahedral coordination environment is shown below. Given this diagram, and the axes in
the accompanying picture, identify which d orbitals are found at which level. In the picture, the metal atom is at the center of
the cube, and the circle represent the ligands.

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 Figure 4.1.2.17 :

Answer
The three orbitals shown above interact a little more strongly with the ligands. The three orbitals shown below interact a
little more weakly.

The reason for the difference in the interaction has to do with how
close the nearest lobe of a d orbital comes to a ligand. There are really two possible positions: the face of a cube or the edge
of a cube. If the ligands are at alternating corners of the cube, then the orbitals pointing at the edges are a little closer than
those pointing at the faces of the cube.

 Exercise 4.1.2.3

Typically, the d orbital splitting energy in the tetrahedral case is only about 4/9 as large as the splitting energy in the analogous
octahedral case. Explain why it is smaller for the tetrahedral case.

Answer

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 The ligands do not overlap with the d orbitals as well in tetrahedral complexes as they do in octahedral complexes. Thus,
there is a weaker bonding interaction in the tetrahedral case. That means the antibonding orbital involving the d electrons is
not raised as high in energy, so the splitting between the two d levels is smaller.

 Exercise 4.1.2.4

Suppose each of the ions in Exercise 4.1.2.1 (CC8.1) were in tetrahedral, rather than octahedral, coordination environments.
Draw the d orbital diagrams for the high spin and the low spin case for each ion.

Answer a)

Answer b)

Answer c)

Answer d)

Answer e)

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Answer f)

Answer g)

 Exercise 4.1.2.5

Usually, tetrahedral ions are high spin rather than low spin. Explain why.

Answer
Because the d orbital splitting is much smaller in the tetrahedral case, it is likely that the energy required to pair two
electrons in the same orbital will be greater than the energy required to promote an electron to the next energy level. In
most cases, the complex will be high spin.

 Exercise 4.1.2.6
The d orbital splitting diagram for a square planar environment is shown below. Given this diagram, and the axes in the
accompanying picture, identify which d orbitals are found at which level.

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 Figure 4.1.2.18 :

Answer
The orbitals are shown in order of energy.

 Exercise 4.1.2.7

Predict whether each compound will be high or low spin.

a. [Fe(py)6]2+
b. [Fe(H2O)6]2+
c. [FeBr6]3-
d. [Co(NH3)6]3+

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e. [Cu(NH3)6]2+
f. [Rh(CO)6]3+
g. [Cr(CO)6]3+
h. [PtCl6]2-

Answer a)
[Fe(py)6]2+ 3d metal, M+2, pi acceptor ligand → low spin
Answer b)
[Fe(H2O)6]2+ 3d metal, M+2, pi donor ligand → high spin
Answer c)
[FeBr6]3- 3d metal, M+3, pi donor ligand → high spin
Answer d)
[Co(NH3)6]3+ 3d metal, M+3, sigma donor ligand → low spin
Answer e)
[Cu(NH3)6]2+ 3d metal, M+2, sigma donor ligand → low spin
Answer f)
[Rh(CO)6]3+ 4d metal, M+3 → low spin
Answer g)
[Cr(CO)6]3+ 3d metal, M+3, pi acceptor ligand → low spin
Answer h)
[PtCl6]2- 5d metal, M+4 → low spin

 Exercise 4.1.2.8
Predict whether each compound will be square planar or tetrahedral.
a. [Zn(NH3)4]2+
b. [NiCl4]2+
c. [Ni(CN)4]2-
d. [Ir(CO)(OH)(PCy3)2]2+ ; Cy = cyclohexyl
e. [Ag(dppb)2]+ ; dppb = 1,4-bis(diphenylphosphino)butane
f. PtCl2(NH3)2
g. PdCl2(NH3)2
h. [CoCl4]2–
i. Rh(PPh3)3Cl

Answer a)
[Zn(NH3)4] 2+ 3d metal, d10, sigma donor ligand → tetrahedral
Answer b)
[NiCl4] 2+ 3d metal, d8, pi donor ligand → tetrahedral
Answer c)
[Ni(CN)4] 2- 3d metal, d8, pi acceptor ligand → square planar
Answer d)

4.1.2.14 https://chem.libretexts.org/@go/page/205592
 [Ir(CO)(OH)(PCy3)2] 2+ 5d metal, d8 → square planar
Answer e)
[Ag(dppb)2]1+ 4d metal, d10, sigma donor ligand → tetrahedral
Answer f)
[PtCl2(NH3)2] 5d metal, d8 → square planar
Answer g)
[PdCl2(NH3)2] 4d metal, d8, M+2, sigma donor ligand → square planar
Answer h)
[CoCl4] 2– 3d metal, d7, sigma donor ligand → tetrahedral
Answer i)
[Rh(PPh3)3Cl] 5d metal, d8 → square planar

Attribution
Chris P Schaller, Ph.D., (College of Saint Benedict / Saint John's University)

4.1.2: Introduction to Ligand Field Theory (Octahedral complexes) is shared under a not declared license and was authored, remixed, and/or
curated by LibreTexts.

4.1.2.15 https://chem.libretexts.org/@go/page/205592
2018/2019 Coordination Chemistry Dr. Asia Hameed

Crystal Field Theory (CFT)

As originally developed, crystal field theory was used to describe the electronic structure of
metal ions in crystals, where they are surrounded by oxide ions or other anions that create an
electrostatic field with symmetry dependent on the crystal structure. The energies of the d
orbitals of the metal ions are split by the electrostatic field, and approximate values for these
energies can be calculated.

CFT was developed in 1930s. Shortly afterward, it was recognized that the same arrangement of
charged or neutral electron pair donor species around a metal ion existed in crystals and
coordination complexes.

In order to understand clearly the interactions that are responsible for crystal or ligand field
effects in transition metal complexes, it is necessary to know the geometrical relationships of
the d orbitals. There are five wave functions that can be written for orbitals having the typical
four-lobed form.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

Crystal Field Effects in Octahedral Complexes

When the d orbitals of a metal ion are placed in an octahedral field of ligand electron pairs,
directed at the surrounding ligands, are raised in energy. The d xy, dxz, and dyz orbitals, which are
directed between the surrounding ions, are relatively unaffected by the field. The resulting
energy difference is identified as o( o for octahedral; some older references use the term 10Dq
instead of o).

In case of free metal ion all the five d-orbitals are degenerate (these have the same energy).
Now consider an octahedral complex, [ML6]n+ in which the central metal cation, Mn+ is placed
at the center of the octahedral and is surrounded by six ligands which reside at the six corners of
the octahedral.

Now suppose both the ligands on each of the three axes are allowed to approach towards the
metal cation, Mn+ from both the ends of the axes. In this process the electrons in d-orbitals of
the metal cation are repelled by the negative point charge or by the negative end of the dipole of
the ligands. (Remember CFT the ionic ligands as negative point charges and neutral ligands as
dipoles). This repulsion will raise the energy of all the five d-orbitals. Since the lobes of dz2 and
dx2-y2 orbitals (eg orbitals) lie directly in the path of the approaching ligands, the electrons in
these orbitals experience greater force of repulsion than those in d xy, dyz, and dzx orbitals

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2018/2019 Coordination Chemistry Dr. Asia Hameed

(t2g orbitals) whose lobes are directed in space between the path of the approaching ligands (the
energy of eg orbitals is increased while that of t2g is decreased (greater the repulsion, greater the
increase in energy).

Thus we find that under the influence of approaching ligands, the five d-orbitals which were
originally degenerate in free metallic cation are now split (or resolved) into two levels, t 2g level
which is triply degenerate and is of lower energy, and eg level which is doubly degenerate and is
of higher energy.

The resulting energy difference is identified as o (o for octahedral) or 10Dq. This approach
provides a simple means of identifying the d- orbital splitting found in coordination complexes
and can be extended to include more quantitative calculations.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

To gain some appreciation for the magnitude of o and how it may be measured, let us
consider the d1 complex, [Ti(H2O)6]3+. This ion exists in aqueous solution of Ti3+ and gives rise
to a purple color. The single d electron in the complex will occupy the lowest energy orbital
available to it (one of the three degenerate t2g orbitals). The purple color is the result of
absorption of light and promotion of the t 2g electron to the eg level. The transition can be
represented as t12geg t02ge1g

The absorption spectra of [Ti(H2O)6]3+ reveals that this transition occurs with a maximum at
20300 cm-1 of energy for o.

The d1 case is the simplest possible because the observed spectral transition reflects the
actual energy difference between the eg and t2g levels.

Crystal Field Stabilization Energy (CFSE)

In the d1 case discussed above , the electron occupies a t 2g orbital, which has an energy of
- 0.4 o relative to the barycenter of the d orbitals. The complex can thus be said to be stabilized
to the extent of 0.4 o compared to the hypothetical spherical-field case. This quantity is termed
the crystal field stabilization energy (CFSE).

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2018/2019 Coordination Chemistry Dr. Asia Hameed

For d2 and d3 metal ions, we would expect the electrons to obey Hund’s rule and thus to occupy
different degenerate t2g orbitals and to remain unpaired. The resulting configuration, t22g and t32g,
will have CFSE of - 0.8 o and - 1.2 o respectively.

When one more is added to form the d4 case, two possibilities arise: either the electron may
enter the higher energy eg level or it may pair with another electron in one of the t 2g orbitals.
The actual configuration adopted will, of course, be the lowest energy one and will depend on
the relative magnitudes of o and P, the energy necessary to cause electron pairing in a single
orbital.

For o< P (the weak field or high spin condition), the fourth electron will enter one of the e g
orbitals rather than of pairing with one in a t2g orbital. The configuration will be t32ge1g and the
net CFSE will be

CFSE = (3 x - 0.4 o) + (1 x + 0.6 o) = - 0.6 o

The addition of a fifth electron to a weak field complex gives a configuration t 32g e2g and a
CFSE of zero. The two electrons in the unfavorable e g level exactly balance the stabilization
associated with three in the t2g level.

If the splitting of d orbitals is large with respect to the pairing energy ( o > P ), it more
favorable for electrons to pair in the t2g level than to enter the strongly unfavorable eg level. In
these strong field or low spin complexes, the eg level remains unoccupied for d1 through d6 ions.
As a result, the CFSE of the complexes having four to seven d electrons will be greater for
strong field than for weak field cases.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

Pairing Energy ( P )
The electron-pairing energy is composed of two terms. One is the coulombic repulsion that
must be overcome when forcing two electrons to occupy the same orbital. The second factor of
importance is the loss of exchange energy that occurs as electrons with parallel spins are forced
to have the antiparallel spins. The exchange energy for a given configuration is proportional to
the number of pairs of electrons having parallel spin.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

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2018/2019 Coordination Chemistry Dr. Asia Hameed

Factors Affecting the Magnitude of

1- Oxidation state of the metal ion
The magnitude of increases with increasing ionic charge on the central metal ion.
The cations from atoms of the same transition series and having the same oxidation
state have almost the same value of but the cation with a higher oxidation state has a
larger value of than that with lower oxidation state
2+ -1 6
o for [Fe(H2O)6] = 10,400 cm ………3d
3+ -1 5
o for [Fe(H2O)6] = 13,700 cm ………3d

o for [Co(H2O)6]2+ = 9,300 cm-1 ……….3d7

3+ -1 6
ofor [Co(H2O)6] = 18,200 cm ………3d
This effect is probably due to the fact that the central ion with higher oxidation state
(higher charge) will polarize the ligands more effectively and thus the ligands would
approach such a cation more closely than they can do the cation of lower oxidation
state, resulting in larger splitting.

2- Nature of the metal ion

Significant differences in also occur for analogous complexes within a given group,
the trend being 3d 4d 5d.
In progressing from Cr to Mo or Co to Rh, the value of increases by as much as
50%. Likewise, the values for Ir complexes are some 25% greater than for Rh
complexes.
3+ -1 6
o for [Co(NH3)6] = 23,000 cm …….3d
3+ -1 6
o for [Rh(NH3)6] = 34,000 cm ……4d
3+ -1
o for [Ir(NH3)6] = 41,000 cm ……5d6

An important result of this trend is that complexes of the second and third transition
series have a much greater tendency to be low spin than do complexes of the first
transition series.

3- Number and geometry of the ligands

The point-charge model predicts that for a tetrahedral complex will be only about
50% as large as for an octahedral complex, all other factors being equal. This
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2018/2019 Coordination Chemistry Dr. Asia Hameed

approximate relationship is observed for VCl4 and [VCl6]2- , as well as for [Co(NH3)4]2+
and [Co(NH3)6]2+. (The crystal field splitting in a tetrahedral field is smaller than that in
an octahedral field. For the same metal ion, ligands and metal-ligand distances,
( t = 4/9 o.)

4- Nature of the ligands

The magnitude of varies from strong to weak ligands. Strong ligands are those which
exert a strong field on the central metal ion and hence have higher splitting power
consequently relatively lower splitting power. Thus strong ligands (e.g. CN -) give larger
value of and weak ligands (e.g. F-) yield a smaller value of .
Based on similar data of the absorption spectra for a wide variety of complexes, it is
possible to list ligands in order of increasing field strength in a spectrochemical series.

The common ligands can be arranged in the order of their increasing splitting power to
cause d-splitting. This series called spectrochemical series.

This series shows that the value of in the series also increases from left to right.
The order of field strength of the common ligands shown above is independent of the
nature of the central metal ion and the geometry of the complex.

Although the spectrochemical series and other trends described in this section allow one to
rationalized differences in spectra and permit some predictability, they present serious
difficulties in interpretation for crystal field theory. If the splitting of the d orbitals resulted
simply from the effect of point charges (ions or dipoles), one should expect that anionic ligands
would exert the greatest effect. To the contrary, most anionic ligands lie at the low end of the
spectrochemical series. Furthermore, OH- lies below the neutral H2O molecule and NH3
produces a greater splitting than H2O, although the dipole moment in the reverse order

These apparent weaknesses in the theory called into question the assumption of purely
electrostatic interactions between ligands and central metal ions and led eventually to the
development of bonding description that include covalent interactions between ligands
and metal.
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2018/2019 Coordination Chemistry Dr. Asia Hameed

CFT for Tetrahedral Complexes

Let us consider a tetrahedral complex ion, [ML4]n+ in which the central metal ion (Mn+) is
surrounded by four ligands.

A tetrahedron may be supposed to have been formed from a cube. The center of the cube is the
center of the tetrahedron at which is placed the central metal ion (Mn+). Four alternate corners of
the cube are the four corners of the tetrahedron at which the four ligands, L are placed. The four
ligands are lying between the three axes x,y and z which pass through the centers of the six
faces of the cube and thus go through the center of the cube. Now since the lobes of t2 orbitals
(dxy, dyz and dzx) are lying between the axes (are lying directly in the path of the ligands), these
orbitals will experience greater force of repulsion from the ligands than those of e orbitals (dz2
and dx2-y2) whose lobes are lying along axes (are lying in space between the ligands).

Thus the energy of t2 orbitals will be increased while that of e orbitals will be decreased.
Consequently the d orbitals are again split into two sets.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

The energy difference between t2 and e sets for tetrahedral complex is represented as t

The crystal field splitting in a tetrahedral field is smaller than that in an octahedral field because
in an octahedral complex there is a ligand along each axis and in a tetrahedral complex no
ligand lies directly along any axis. For this reason and also because there are only four ligands
in the tetrahedral complex, while in an octahedral complex there are six ligands, the tetrahedral
orbital splitting, t is less than o for the same metal ion, ligands and metal-ligand distances,

t= 4/9 o

As a result, orbital splitting energies in tetrahedral complexes generally are not large enough to
force electrons to pair, and low spin configurations are rarely observed.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

Crystal Field Splitting of d-orbitals in Tetragonal and Square Planar

Complexes
If two trans ligands in an octahedral ML6 complex (for example those along the z axis) are
moved either towards or away from the metal ion, the resulting complex is said to be
tetragonally distorted. Ordinarily such distortions are not favored since they result in a net of
loss of bonding energy. In certain situation, however, such a distortion is favored because of
Jahn-Teller effect.

A complex of general formula trans-MA2B4 also will have tetragonal symmetry. For now, we
will merely consider the limiting case of tetragonal elongation, a square planar ML4 complex,
for the purpose of deriving its d orbital splitting pattern.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

The figure bellow illustrates the effect of z-axis stretching on the eg and t2g orbitals in an
octahedral complex. Orbitals having a z component (the dz2, dxz and dyz ) will experience a
decrease in electrostatic repulsion from the ligands and will therefore be stabilized. At the same
time, the “non-z” orbitals will be raised in energy, with the barycenter remaining constant. The
overall result is that the eg level is split into two levels, an upper (dx2-dz2) and a lower (dz2) and
the t2g set is split into (dxy) and a doubly degenerate (dxz, dyz).

The energy spacing between the (dxy) and (dx2-dy2) levels is defined as . As in the octahedral
case, this splitting is equal to 10Dq.

The square planar geometry is favored by metal ions having a d 8 configuration in the presence
of a strong field. This combination gives low spin complexes with the eight d electrons
occupying the low-energy dxz, dyz, dz2, and dxy orbitals, while the high-energy dx2-y2 orbital
remains unoccupied. The stronger the surrounding field, the higher the d x2- y2 orbital will be
raised. As long as this level is unoccupied, however , the overall effect on the complex will be
stabilization because the lower, occupied orbitals will drop in energy by corresponding amount.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

Typical low spin square planar complexes are [Ni(CN)4]2- , [PdCl4]2- , [Pt(NH3)4]2+ ,
[PtCl4]2- , and [AuCl4]- , all d8 species.

The Jahn-Teller Effect

The Jahn-Teller theorem states that there cannot be unequal occupation of orbitals with identical
energies. To avoid such unequal occupation, the molecule distorts so that these orbitals are no
longer degenerate. For example, octahedral Cu(II), a d9 ion, would have three electrons in the
two eg levels without the Jahn-Teller effect, as in the center of the Figure bellow. The Jahn-
Teller effect requires that the shape of the complex change slightly, resulting in a change in the
energies of the orbitals. The resulting distortion is most often an elongation along one axis, but
compression along one axis is also possible.

In octahedral complexes, where the eg orbitals are directed towards the ligands, distortion of the
complex has a larger effect on these energy levels and a smaller effect when the t2g orbitals are
involved.

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2018/2019 Coordination Chemistry Dr. Asia Hameed

Examples of significant Jahn-Teller are found in complexes :

d4 high spin (weak ligands) Cr(II) and Mn(III)

d7 low spin (strong ligands) Co(II) and Ni(III)

d9 (strong or weak ligands) Cu(II) and Ag(II)

Limitation of CFT
1- CFT considers only the metal ion d-orbitals and gives no consideration at all to other
metal orbitals such as s, px , py , and pz orbitals and the ligand orbitals. Therefore, to
explain all the properties of the complexes dependent on the π-ligand orbitals will be
outside the scope of CFT. CFT does not consider the formation of π-bonding in
complexes.
2- CFT is unable to account satisfactorily for the relative strengths of ligand, e.g. , it gives
no explanation as to why H2O appears in the spectrochemical series as a stronger ligand
than OH- .
3- According to CFT, the bond between the metal and ligand is purely ionic, It gives no
account of the partly covalent nature of the metal-ligand bonds.

15
5.6: Crystal Field Stabilization Energy, Pairing, and Hund's Rule
The splitting of the d-orbitals into different energy levels in transition metal complexes has important consequences for their
stability, reactivity, and magnetic properties. Let us first consider the simple case of the octahedral complexes [M(H2O)6]3+, where
M = Ti, V, Cr. Because the complexes are octahedral, they all have the same energy level diagram:

The Ti3+, V3+, and Cr3+ complexes have one, two and three d-electrons respectively, which fill the degenerate t2g orbitals singly.
The spins align parallel according to Hund's rule, which states that the lowest energy state has the highest spin angular momentum.
For each of these complexes we can calculate a crystal field stabilization energy, CFSE, which is the energy difference between
the complex in its ground state and in a hypothetical state in which all five d-orbitals are at the energy barycenter.
For Ti3+, there is one electron stabilized by 2/5 ΔO, so C F SE = −(1)( 2

5
)(ΔO ) =
−2

5
ΔO

Similarly, CFSE = -4/5 ΔO and -6/5 ΔO for V3+ and Cr3+, respectively.
For Cr2+ complexes, which have four d-electrons, the situation is more complicated. Now we can have a high spin configuration
(t2g)3(eg)1, or a low spin configuration (t2g)4(eg)0 in which two of the electrons are paired. What are the energies of these two
states?
High spin: C F SE = (−3)( 2

5
)ΔO + (1)(
3

5
)ΔO = −
3

5
ΔO

Low spin: C F SE = (−4)( 2

5
)ΔO + P = −
8

5
ΔO + P , where P is the pairing energy
Energy difference = -ΔO + P
The pairing energy P is the energy penalty for putting two electrons in the same orbital, resulting from the electrostatic repulsion
between electrons. For 3d elements, a typical value of P is about 15,000 cm-1.
The important result here is that a complex will be low spin if ΔO > P, and high spin if ΔO < P.
Because ΔO depends on both the metals and the ligands, it determines the spin state of the complex.
Rules of thumb:
3d complexes are high spin with weak field ligands and low spin with strong field ligands.
High valent 3d complexes (e.g., Co3+ complexes) tend to be low spin (large ΔO)
4d and 5d complexes are always low spin (large ΔO)
Note that high and low spin states occur only for 3d metal complexes with between 4 and 7 d-electrons. Complexes with 1 to 3 d-
electrons can accommodate all electrons in individual orbitals in the t2g set. Complexes with 8, 9, or 10 d-electrons will always
have completely filled t2g orbitals and 2-4 electrons in the eg set.

5.6.1 https://chem.libretexts.org/@go/page/183322
 d-orbital energy diagrams for high and low spin Co2+ complexes, d7

Examples of high and low spin complexes:

[Co(H2O)62+] contains a d7 metal ion with a weak field ligand. This complex is known to be high spin from magnetic susceptibility
measurements, which detect three unpaired electrons per molecule. Its orbital occupancy is (t2g)5(eg)2.
We can calculate the CFSE as −(5)( 2

5
)ΔO + (2)(
3

5
)ΔO = −
4

5
ΔO

[Co(CN)64-] is also an octahedral d complex but it contains CN-, a strong field ligand. Its orbital occupancy is (t2g)6(eg)1 and it
7

therefore has one unpaired electron.

In this case the CFSE is −(6)( 2

5
)ΔO + (1)(
3

5
)ΔO + P = −
9

5
ΔO + P .

Magnetism of transition metal complexes

Compounds with unpaired electrons have an inherent magnetic moment that arises from the electron spin. Such compounds
interact strongly with applied magnetic fields. Their magnetic susceptibility provides a simple way to measure the number of
unpaired electrons in a transition metal complex.

If a transition metal complex has no unpaired electrons, it is diamagnetic and is weakly repelled from the high field region of an
inhomogeneous magnetic field. Complexes with unpaired electrons are typically paramagnetic. The spins in paramagnets align
independently in an applied magnetic field but do not align spontaneously in the absence of a field. Such compounds are attracted
to a magnet, i.e., they are drawn into the high field region of an inhomogeneous field. The attractive force, which can be measured
with a Guoy balance or a SQUID magnetometer, is proportional to the magnetic susceptibility (χ) of the complex.

The effective magnetic moment of an ion (µeff), in the absence of spin-orbit coupling, is given by the sum of its spin and orbital
moments:
μeff = μspin + μorbital = μs + μL (5.6.1)

In octahedral 3d metal complexes, the orbital angular momentum is largely "quenched" by symmetry, so we can approximate:
μeff ≈ μs (5.6.2)

We can calculate µs from the number of unpaired electrons (n) using:

−−−−−−−
μef f = √ n(n + 2) μB (5.6.3)

Here µB is the Bohr magneton (= eh/4πme) = 9.3 x 10-24 J/T. This spin-only formula is a good approximation for first-row
transition metal complexes, especially high spin complexes. The table below compares calculated and experimentally measured
values of µeff for octahedral complexes with 1-5 unpaired electrons.

Number of
Spin-only observed
Ion unpaired
moment /μB moment /μB
electrons

5.6.2 https://chem.libretexts.org/@go/page/183322
 Ti3+ 1 1.73 1.73

V4+ 1 1.68–1.78

Cu2+ 1 1.70–2.20

V3+ 2 2.83 2.75–2.85

Ni2+ 2 2.8–3.5

V2+ 3 3.87 3.80–3.90

Cr3+ 3 3.70–3.90

Co2+ 3 4.3–5.0

Mn4+ 3 3.80–4.0

Cr2+ 4 4.90 4.75–4.90

Fe2+ 4 5.1–5.7

Mn2+ 5 5.92 5.65–6.10

Fe3+ 5 5.7–6.0

The small deviations from the spin-only formula for these octahedral complexes can result from the neglect of orbital angular
momentum or of spin-orbit coupling. Tetrahedral d3, d4, d8 and d9 complexes tend to show larger deviations from the spin-only
formula than octahedral complexes of the same ion because quenching of the orbital contribution is less effective in the tetrahedral
case.
Summary of rules for high and low spin complexes:
3d complexes: Can be high or low spin, depending on the ligand (d4, d5, d6, d7)
4d and 5d complexes: Always low spin, because ΔO is large
Maximum CFSE is for d3 and d8 cases (e.g., Cr3+, Ni2+) with weak field ligands (H2O, O2-, F-,...) and for d3-d6 with strong
field ligands (Fe2+, Ru2+, Os2+, Co3+, Rh3+, Ir3+,...)
Irving-Williams series. For M2+ complexes, the stability of the complex follows the order Mg2+ < Mn2+ < Fe2+ < Co2+ <
Ni2+ < Cu2+ > Zn2+. This trend represents increasing Lewis acidity as the ions become smaller (going left to right in the
periodic table) as well as the trend in CFSE. This same trend is reflected in the hydration enthalpy of gas-phase M2+ ions, as
illustrated in the graph at the right. Note that Ca2+, Mn2+, and Zn2+, which are d0, d5(high spin), and d10 aquo ions,
respectively, all have zero CFSE and fall on the same line. Ions that deviate the most from the line such as Ni2+ (octahedral
d8) have the highest CFSE.

Colors and spectra of transition metal complexes

Transition metal complexes often have beautiful colors because, as noted above, their d-d transition energies can be in the visible
part of the spectrum. With octahedral complexes these colors are faint (the transitions are weak) because they violate the Laporte

5.6.3 https://chem.libretexts.org/@go/page/183322
selection rule. According to this rule, g -> g and u -> u transitions are forbidden in centrosymmetric complexes. d-orbitals have g
(gerade) symmetry, so d-d transitions are Laporte-forbidden. However octahedral complexes can absorb light when they
momentarily distort away from centrosymmetry as the molecule vibrates. Spin flips are also forbidden in optical transitions by the
spin selection rule, so the excited state will always have the same spin multiplicity as the ground state.

The spectra of even the simplest transition metal complexes are rather complicated because of the many possible ways in which the
d-electrons can fill the t2g and eg orbitals. For example, if we consider a d2 complex such as V3+(aq), we know that the two
electrons can reside in any of the five d-orbitals, and can either be spin-up or spin-down. There are actually 45 different such
arrangements (called microstates) that do not violate the Pauli exclusion principle for a d2 complex. Usually we are concerned
only with the six of lowest energy, in which both electrons occupy individual orbitals in the t2g set and all their spins are aligned
either up or down.

From left: [V(H2O)6]2+ (lilac), [V(H2O)6]3+ (green), [VO(H2O)5]2+ (blue) and [VO(H2O)5]3+ (yellow).

We can see how these microstates play a role in electronic spectra when we consider the d-d transitions of the [Cr(NH3)6]3+ ion.
This ion is d3, so each of the three t2g orbitals contains one unpaired electron. We expect to see a transition when one of the three
electrons in the t2g orbitals is excited to an empty eg orbital. Interestingly, we find not one but two transitions in the visible.

The reason that we see two transitions is that the electron can come from any one of the t2g orbitals and end up in either of the eg
orbitals. Let us assume for the sake of argument that the electron is initially in the dxy orbital. It can be excited to either the dz2 or
the dx2-y2 orbital:
dxy → dz 2 (higher energy)
dxy → dx2−y2 (lower energy)
The first transition is at higher energy (shorter wavelength) because in the excited state the configuration is (dyz1dxz1dz21). All three
of the excited state orbitals have some z-component, so the d-electron density is "piled up" along the z-axis. The energy of this
transition is thus increased by electron-electron repulsion. In the second case, the excited state configuration is (dyz1dxz1dx2-y21),
and the d-electrons are more symmetrically distributed around the metal. This effect is responsible for a splitting of the d-d bands
by about 8,000 cm-1. We can show that all other possible transitions are equivalent to one of these two by symmetry, and hence we
see only two visible absorption bands for Cr3+ complexes.

This page titled 5.6: Crystal Field Stabilization Energy, Pairing, and Hund's Rule is shared under a CC BY-SA 4.0 license and was authored,
remixed, and/or curated by Chemistry 310 (Wikibook) via source content that was edited to the style and standards of the LibreTexts platform; a
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5.6.4 https://chem.libretexts.org/@go/page/183322
NCERT Chemistry (Vol 1) Chapter 9 Coordination compounds

CBSE NCERT Solutions for Class 12 chemistry Chapter 9

Exercises

Q.1. Draw the structures of optical isomers of:

CrC2O433-

Solution: When the coordination compounds have the same formula but differ in their ability to rotate directions of the
plane polarised light are said to exhibit optical isomerism and the molecules are optical
isomers. CrC2O433-=Cren33-optical isomers are

Q.2. Draw the structures of optical isomers of PtCl2en22+.

Solution: When the coordination compounds have the same formula but differ in their ability to rotate directions of the
plane polarised light are said to exhibit optical isomerism, and the molecules are optical isomers. These isomers
are mirror images and non-superimposable. They are called enantiomers.

Optical isomers of PtCl2en22+.

Q.3. Draw the structures of optical isomers of CrNH32Cl2en+.

Practice more on Coordination compounds Page 1 www.embibe.com

NCERT Chemistry (Vol 1) Chapter 9 Coordination compounds

Solution: Optical isomers are dextro and laevo, geometrical isomers are cis and trans. This compound has two
geometrical isomers. Out of these two, only cis isomer is optically active, it can form two optical isomers.

Optical isomers of CrNH32Cl2en+ are

Q.4. Explain the bonding in coordination compounds in terms of Werner’s postulates.

Solution: The main postulates of Werner’s theory of coordination compounds are as follows:
(a) Metals possess two types of valencies called

(i) primary valency which is ionisable;

(ii) secondary valency which is non-ionisable.

(b) Primary valency is satisfied by the negative ions, and it is that which a metal exhibits in the formation of its
simple salts.
(c) Secondary valencies are satisfied by neutral ligand or negative ligand and are those which metal exercises in
the formation of its complex ions. Every cation has a fixed number of secondary valencies which are directed in
space about central metal ion in certain fixed directions.

For example: In CoCl3.6NH3, valencies between Co and Cl are primary valencies and valencies between Co
and NH3 are secondary. In CoCl3.6NH3 , six ammonia molecules linked to Co by secondary valencies are
directed to six corners of a regular octahedron and thus account for structure of CoCl3.6NH3 as follows:

Q.5. Draw all the isomers (geometrical and optical) of:

CoCl2en2+

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Solution: Geometrical isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the
ligands. This type of isomerism arises when didentate ligands are present in complexes of formula CoCl2en2+

When the coordination compounds have the same formula but differ in their ability to rotate directions of the
plane of polarised light are said to exhibit optical isomerism and the molecules are optical isomers. Trans-
form is optically inactive, whereas cis form is optically active and shows optical isomerism.

Optical isomers of cis-CoCl2en2+

Q.6. Draw all the isomers (geometrical and optical) of:

CoNH3Clen22+

Solution: Geometrical isomers of CoNH3Clen22+ are cis and trans.

Trans-isomers are optically inactive but Cis-isomers are optically active. Cis isomers form two optical isomers.

Q.7. Draw all the isomers (geometrical and optical) of:

CoNH32Cl2en+

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Solution: CoNH32Cl2en+ optical and geometrical isomers are

Optical isomers are dextro and laevo, geometrical isomers are cis and trans. This compound has two
geometrical isomers. Out of these two, only cis isomer is optically active, it can form two optical isomers.

Q.8. Write all the geometrical isomers of PtNH3BrClPy and how many of these will exhibit optical isomers?

Solution: Three isomers of Pt(NH3)(Br)(Cl)(py) are possible.

These are obtained by keeping the position of one of the ligand, say NH3 fixed and rotating the positions of
others. This type of isomers do not show any optical isomerism. Square planar complexes show optical
isomerism only when square planar complexes have unsymmetrical chelating ligands.

Q.9. Aqueous copper sulphate solution (blue in colour) gives a green precipitate with aqueous potassium fluoride. Explain the
experimental results.

Solution: Aqueous CuSO4 exists as CuH2O4SO4. It is blue in colour due to the presence of CuH2O42+ ions. When
KF is added, the weak H2O ligands are replaced by F– ligands forming [CuF4]2- ions which is a green
precipitate.

CuH2O42++4F-⟶CuF42-Green ppt.+4H2O

Q.10. Aqueous copper sulphate solution (blue in colour) gives a bright green solution with aqueous potassium chloride. Explain
these experimental results.

Solution: Aqueous CuSO4 solution exists as [Cu(H2O)4]SO4 which has blue colour due to [Cu(H2O)4]2+ ions.

When KCl is added, Cl- ligands replace the weak H2O ligands forming CuCl42- ion which has bright green
colour.

CuH2O42++4Cl-→CuCl42-+4H2O

Q.11. What is the coordination entity formed when an excess of aqueous KCN is added to an aqueous solution of copper sulphate?
Why is it that no precipitate of copper sulphide is obtained when H2Sg is passed through this solution?

Solution: CuSO4s+4KCNaq⟶K2CuCN4aq+K2SO4aq
i.e., CuH2O42++4CN-⟶CuCN42-+4H2O
Thus, the coordination entity formed in the process is K2CuCN4. It is a very stable complex, which does not
ionise to give Cu2+ ions when added to water. Hence, Cu2+ ions do not precipitate when H2Sg is passed
through the solution.

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Q.12. Discuss the nature of bonding in the following coordination entity based on valence bond theory: FeCN64-

Solution: FeCN64-
In the coordination complex FeCN64-, iron exists in the +2 oxidation state.
Electronic configuration of Fe2+ is 1s22s22p63s23p63d64s0
Orbitals of Fe2+ ion:

As CN- is a strong field ligand, so the pairing of the unpaired 3d electrons occurs.

Since there are six ligands around the central metal ion, the hybridisation is d2sp3.
d2sp3 hybridised orbitals of Fe2+ are:

Six electron pairs from CN- ions occupy the six hybrid d2sp3 orbitals.
Then,

Hence, the geometry of the complex is octahedral.

The compound does not have unpaired electrons, so the complex is diamagnetic.

Q.13. Discuss the nature of bonding in the following coordination entity based on valence bond theory FeF63-.

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Solution: In this complex, the oxidation state of Fe is +3

Electronic configuration of Fe3+ : 1s22s22p63s23p63d54s0

Orbitals of Fe3+ ions:

There are six F- ligands. As F- is a weak field ligand, it does not cause the pairing of the electrons in
the 3d orbital. Hence, the hybridisation is sp3d2.

Hence, the geometry of the complex is found to be octahedral.

Q.14. Discuss the nature of bonding in the following coordination entity based on valence bond theory CoC2O433-.

Solution: Cobalt exists in +3 oxidation state in the given complex.

Electronic configuration of Co3+is 1s22s22p63s23p63d64s0

Orbitals of Co3+ ion:

Oxalate is a weak field ligand. Therefore, it cannot cause the pairing of the 3d orbital electrons. As there are six
ligands, hybridisation is sp3d2 because it is an outer orbital complex.

The six electron pairs from three oxalate ions (oxalate anion is a bidentate ligand) occupy these sp3d2 orbitals.

Hence, the geometry of the complex is found to be octahedral.

Q.15. Discuss the nature of bonding in the following coordination entity based on valence bond theory CoF63-.

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Solution: Cobalt exists in the + 3 oxidation state.

Electronic configuration of Co3+: 1s22s22p63s23p63d64s0

Orbitals of Co3+ ions:

Again, fluoride ion is a weak field ligand. It cannot cause the pairing of 3d electrons. As a result, the Co3+ion
will undergo sp3d2 hybridisation.

Hence, the geometry of the complex is octahedral.

Q.16. Draw figure to show the splitting of d orbitals in an octahedral crystal field.

Solution:

The splitting of the d orbitals in an octahedral field takes place in such a way that dx2-y2, dz2 experience a rise
in energy and form the eg level, while dxy, dyz and dzx experience a fall in energy and form the t2g level.

Q.17. What is the spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.

Solution: A spectrochemical series is the arrangement of common ligands in the increasing order of their Crystal-Field
Splitting Energy (CFSE) values. The ligands present on the right-hand side of the series are strong field ligands
while that on the light hand side are weak field ligands. Also, strong-field ligands cause higher splitting in the d
orbitals than weak field ligands.
I-<Br-<S2-<SCN-<Cl-<N3-<F-<OH-<C2O42-<H2O<NCS-<CN-<NH3<en<SO32-<NO2-<phen<CO

Q.18. What is crystal field splitting energy? How does the magnitude of ∆o decide the actual configuration of d-orbitals in a
coordination entity?

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Solution: The degenerate d-orbitals (having same energy) split into two energy levels i.e., eg and t2g in the presence of
ligands. Due to the presence of ligands the splitting of the degenerate levels occurs and it is called as crystal-
field splitting while the energy difference between the two levels ( eg and t2g) is called the crystal-field splitting
energy. It is denoted by ∆o for octahedral complexes.

Then the filling of the electrons takes place. After one electron (each) has been filled in the three t2g orbitals,
the filling of the fourth electron takes place in two ways. It can enter the eg orbital (giving rise to t2g3eg1 like
electronic configuration) or the pairing of the electrons can take place in the t2g orbitals (giving rise to t2g4eg0
like electronic configuration). If the ∆o value of a ligand is less than the pairing energy P, then the electrons
enter the eg orbital. On the other hand, if the ∆o value of a ligand is more than the pairing energy P, then the
electrons starts pairing up in the t2g orbital.

Q.19. CrNH363+ is paramagnetic while NiCN42- is diamagnetic. Explain why?

Solution: In CrNH363+, Cr is in the +3 oxidation state.

Electronic configuration of Cr+3 is 1s2, 2s22p6, 3s23p63d3, 4s0

NH3 act as a weak field ligand that does not cause the pairing of the electrons in the 3d orbital.

Therefore, it undergoes d2sp3 hybridisation and the three electrons in the 3d orbitals remain unpaired. Hence, it
is paramagnetic in nature.

In NiCN42-, Ni exists in the +2 oxidation state.

The electronic configuration of Ni+2 is 1s2, 2s22p6, 3s23p63d8, 4s0

CN- is a strong field ligand. It causes the pairing of the 3d orbital electrons. Then, Ni2+ undergoes dsp2
hybridisation.

As there are no unpaired electrons, it is diamagnetic.

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Q.20. FeSO4 solution mixed with NH42SO4 solution in 1:1 ratio gives the test of Fe2+ ion but CuSO4 solution mixed with
aqueous ammonia in 1:4 molar ratio does not give the test of Cu2+ ion. Explain why?

Solution: NH42SO4+FeSO4+6H2O→FeSO4.NH42SO4.6H2O (Mohr Salt)

CuSO4+4NH3+5H2O→CuNH34SO4.5H2O
FeSO4.NH42SO4.6H2O and CuNH34SO4.5H2O, the former is an example of a double salt, while the latter is
a coordination compound.
A double salt is a compound that is stable in the solid-state but breaks up into ions in the dissolved state. These
compounds exhibit individual properties of their constituents.
For example: FeSO4.NH42SO4.6H2O breaks into Fe2+,NH4+ and SO42- ions. Hence, it gives a positive test
for Fe2+ ions.
However, the individual properties of the constituents are lost. This happens because CuNH34SO4.5H2O does
not show the test for Cu2+. The ions present in the solution of CuNH34SO4.5H2O are CuNH342+ and SO42-.

Q.21. A solution of NiH2O62+ is green but a solution of NiCN42- is colourless. Explain.

Solution: NiH2O6+2 consists of Ni+2 ion with 3d8 electronic configuration. In this configuration, there are two unpaired
electrons which cannot pair up because H2O is a weak ligand. Thus, the d-d transition absorbs the incoming
light and it emits a green light. Thereby, giving a green colour to the solution.

NiCN4-2 consists of Ni+2 ion with 3d8 electronic configuration. But, CN-is present here, which is a strong
ligand and in its presence, the unpaired electrons pair up. Thus, there is no d-d transition so no colour.

Q.22. FeCN64- and FeH2O62+ are of different colours in dilute solutions. Why?

Solution: The colour of a particular coordination compound depends on the magnitude of the Crystal-Field Splitting
Energy (∆o). This CFSE, in turn, depends on the nature of the ligand. In the case of FeCN64- and
FeH2O62+, the colour differs because there is a difference in the CFSE. CN- is a strong field ligand having a
higher CFSE value as compared to the CFSE value of water. This means that the absorption of energy for the
intra d- d transition also differs.
Hence, the transmitted colour also differs.

Q.23. Discuss the nature of bonding in metal carbonyls.

Solution: The metal-carbon bonds in metal carbonyls have both σ and π bond characters. When the carbonyl carbon
donates a lone pair of electrons to the vacant orbital of the metal then σ bond is formed. A π bond is formed by
the donation of a pair of electrons from the filled metal d orbital into vacant anti-bonding π* orbital (also
known as back bonding of the carbonyl group). The σ bond strengthens the π bond and vice-versa. This
synergic effect strengthens the bond between CO and the metal.

Q.24. Give the oxidation state, d-orbital occupation and coordination number of the central metal ion in the following
complex: K3CoC2O43

Solution: K3CoC2O43
The central metal ion is Co. Let its oxidation state =x
C2O4-2 oxalate ion is negative ligand its oxidation state =-2
Oxidation state of potassium =+1
The C2O4-2 oxalate ion is a bidentate ligand.
Oxidation state of central atom can be given as:
x+3×-2=-3
x=+3

C2O4-2 oxalate ion is a bidentate ligand and there are three in the complex. So, the coordination number of the
complex is 6.
C2O4-2, oxalate ion is weak field ligand, so the d orbital occupation for Co3+ is t2g6 eg0.

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Q.25. Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complex:

cis-Cren2Cl2Cl

Solution: The central metal atom is Cr

Let its oxidation state of Cr =x
Chloride ion is negatively charged ligand and its oxidation state is -1
(en) is a neutral ligand and its oxidation state =0
The oxidation state of central metal can be given as:
x+20+2-1=+1x-2=+1x=+3

Chloride ion is a monodentate ligand and ethylene diamine is a bidentate ligand. Hence, totally six atoms
combining with central metal from all ligands. So the coordination number is 6.

The d orbital occupation for Cr3+ is t2g3.

Q.26. Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complex:

NH42CoF4

Solution: The central metal atom is Co

Let its oxidation state of Co=x
Fluoride ion is a negatively charged ligand and its oxidation state =-1.

Ammonium ion NH4+1 is a positively charged ion and its oxidation state is +1.
The oxidation state of cobalt can be given as

X+-1×4=-2X=+2
Cobalt combines with four ligands(Fluoride) in the coordination sphere. Fluoride ion is a mono-dentate ligand.
So the coordination number of cobalt is 4.
The d-orbital occupation for Co2+is eg4 t2g3.

Q.27. Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complex

MnH2O6SO4

Solution: The central metal atom is Mn

Let its oxidation state of Mn = x
Water H2O is a neutral ligand and its oxidation state =0
Sulphate SO4-2 is negatively charged ion and its oxidation state =-2
Manganese combines with six water molecules and water is a mono-dentate ligand. So, the coordination
number of the compound is 6.
The oxidation state of manganese can be given as:

x+60=+2x=+2
The d orbital occupation for Mn+2 is t2g3 eg2.

Q.28. Write down the IUPAC name for each of the following complex and indicate the oxidation state, electronic configuration
and coordination number. Also, give stereochemistry and magnetic moment of the complex:
KCrH2O2C2O42.3H2O

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Solution: In the compound, the central metal ion is chromium. The ligands present are water H2O, oxalate
ionC2O42- which are named as 'diaqua' and 'dioxalo' due to the presence of two molecules each. Water is a
neutral ligand with an oxidation state of zero and that of oxalate ion is -2. The oxidation number of potassium
is +1. The oxidation number of chromium is calculated as:

+1 + x + 20 + 2-2 + 30 = 0x = +3

The IUPAC name of the compound is; Potassium diaquadioxalatochromate (III) trihydrate.
Oxidation state of chromium =+3
Electronic configuration of Cr+3: 1s2 2s2 2p6 3s2 3p6 3d3 or t2g3
Coordination number =6
3d 4s 4pCr ↑↑↑↑↑ ↑ Cr+3 ↑↑↑

As oxalate is a bidentate ligand, the 6 orbitals are occupied by 2 oxalate ions and 2 water molecules
giving d2sp3 hybridisation and with octahedral geometry.

Magnetic moment, μ=nn+2

=33+2
=15
=3.872 BM

Q.29. Write down the IUPAC name for the following complex and indicate the oxidation state, electronic configuration and
coordination number. Also, give stereochemistry and magnetic moment of the complex:

CoNH35ClCl2

Solution: IUPAC name: Pentaamminechlorocobalt (III) chloride

Oxidation state of Co=+3
Coordination number of central atom =6
Shape: octahedral
Electronic configuration of Co+3:1s2 2s2 2p6 3s2 3p6 3d6 i.e t2g6

Stereochemistry:

Magnetic moment can be calculated by using the formula,μ=nn+2 Here, n is the number of unpaired electrons
in the complex.μ=44+2 =24 =4.90 BM

Q.30. Write down the IUPAC name of the following complex and indicate the oxidation state, electronic configuration and
coordination number. Also, give stereochemistry and magnetic moment of the complex:

CrCl3py3

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Solution: CrCl3py3

In the given compound, the central metal atom present is chromium. The ligands present are chlorine Cl- and
pyridinepy. They are named as Trichlorido and tripyridine due to the presence of three molecules each based on
alphabetical order. The pyridine is a neutral ligand with zero oxidation state and that of chlorine is -1. The
oxidation state of chromium in the complex is calculated as:

x + 3-1 + 30 = 0x = +3

Therefore, the IUPAC name is Trichloridotripyridinechromium (III).

Oxidation state of chromium=+3
Electronic configuration for d orbital =t2g3
Coordination number=6

3d 4s 4pCr ↑↑↑↑↑ ↑ Cr+3 ↑↑↑

As pyridine is a bidentate ligand, the 6 orbitals are occupied by 2 pyridine ions and 2
chlorine ions giving d2sp3 hybridisation and with octahedral geometry. Magnetic moment can be calculated by
using the formula, μ=nn+2 Here, nis number of unpaired electrons in the complex. μ=33+2 =15 =4 B.M

Q.31. Write down the IUPAC name of the following complex and indicate the oxidation state, electronic configuration and
coordination number. Also, give stereochemistry and magnetic moment of the complex:

CsFeCl4

Solution: IUPAC name: Caesium tetrachloroferrate (III)

Oxidation state of Fe=+3
Electronic configuration of d5 = eg2t2g3
Coordination number=4
Shape of the complex is tetrahedral

Stereochemistry: optically inactive

Magnetic moment can be calculated by using the formula,

μ=nn+2 Here, n is the number of unpaired electrons in the complex. μ=55+2 =35 =5.91 B.M

Q.32. Write down the IUPAC name of the following complex and indicate the oxidation state, electronic configuration and
coordination number. Also, give stereochemistry and magnetic moment of the complex:

K4MnCN6

Solution: IUPAC name is Potassium hexacyanomanganate (II)

The oxidation state of manganese is +2
Electronic configuration: d5 = t2g5
Coordination number=6

Shape of the complex is octahedral.

Stereochemistry: optically inactive

Magnetic moment

μ=nn+2 =11+2 =3 =1.732 BM

Q.33. Explain the violet colour of the complex TiH2O63+on the basis of crystal field theory.

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Solution: In the complex TiH2O63+, the Ti has the electronic configuration [Ar] 3d2. In [Ti(H2O)6]3+ complex it is
present as Ti3+ which has one unpaired electron in 3d orbital. Thus, d-d transition is possible only in
[Ti(H2O)6]3+ and thereby it shows colour. And also it undergoes d2sp3 (octahedral) hybridization to
accommodate 6 pairs of water. So, the complex is octahedral in shape, will be coloured and paramagnetic due to
presence of one unpaired electron. This unpaired electron is excited from t2g level to eg level by absorbing
yellow light and hence appears violet coloured.

Q.34. What is meant by the chelate effect? Give an example.

Solution: Chelate effect represents the stabilisation of coordination compounds due to formation of metal chelates.
Complexes containing chelating ligands are more stable than complexes containing unidentate ligands.
Thus, [Co(en)3]+3 is more stable than [Co(NH3)6]+3. Here, en is ethylene diammine, a bidentate ligand.

Q.35. Discuss briefly the role of coordination compounds in the biological system.

Solution: Biological system:

(i) Haemoglobin the red blood cell which acts as oxygen carrier to different parts of the body is a complex of
iron(II).

(ii) Vitamin B12 is a complex of cobalt metal. Trace metals also function through coordination processes. (iii)
A complex of zinc(II) called enzyme CPA helps in digestion of food. (iv) The chlorophyll, the green colouring
plant pigment that plays an important role in photosynthesis is a complex of magnesium. In chlorophyll Mg is
coordinated to four nitrogens of porphyin units.

Q.36. Explain the role of coordination compounds in medicinal chemistry?

Solution: There is growing interest in the use of chelation therapy in medicinal chemistry. An example is the treatment of
problems caused by the presence of metals in toxic proportions in plant/animal systems. Thus, excess of copper
and iron are removed by the chelating ligands D-penicillamine and desferrioxamine B via the formation of
coordination compounds.

To remove metal poisoning, complexing agents are used, cis platin [PtCl2(NH3)2] is used in cancer
chemotherapy. It effectively inhibit the growth of tumours. EDTA is used in the treatment of lead poisoning.
Inside the body, calcium in the complex is replaced by lead. The more soluble lead-EDTA complex is
eliminated in urine.

Q.37. Explain the role of coordination compounds in analytical chemistry.

Solution: Coordination compounds find use in many qualitative and quantitative chemical analysis. The familiar colour reactions
given by metal ions with a number of ligands (especially chelating ligands), as a result of the formation of coordination
entities, form the basis for their detection and estimation by classical and instrumental methods of analysis. Examples of
such reagents include EDTA, DMG (dimethylglyoxime), α-nitroso- β-naphthol, cupron, etc.

Q.38. The role of coordination compounds in extraction/metallurgy of metals.

Solution: Some important extraction processes of metals, like those of silver and gold, make use of complex formation.
Gold, for example, combines with cyanide in the presence of oxygen and water to form the coordination
entity AuCN2- in aqueous solution. Gold can be separated in metallic form from this solution by the addition of
zinc.

Q.39. How many ions are produced from the complex [CoNH36]Cl2 in solution?
643

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Solution: The given complex can be ionised as CoNH36Cl2→CoNH36+2 +2Cl-

Thus, one CoNH36+2 along with two Cl- ions are produced. So, a total of three ions are produced.

Q.40. Amongst the following ions which one has the highest magnetic moment value?

CrH2O63+FeH2O62+

Solution: In CrH2O63+, H2O is a weak field ligand.

The oxidation state of Cr=+3.

Electronic configuration of Cr3+ =1s22s22p63s23p63d3. Number of unpaired electrons in CrH2O63+=3.

Magnetic moment μ=nn+2=33+2=15=3.87 BM In FeH2O62+, H2O is a weak field ligand. The oxidation
number of Fe in the complex is +2. Coordination Number =6 Electronic configuration
of Fe2+ is 1s22s22p63s23p63d64s0. Number of unpaired electrons =4.
Magnetic moment μ=44+2 =24 =4.89 BM In ZnH2O62+, H2O is a weak field ligand. The oxidation state
of Zn=+2. Electronic configuration of Zn+2 is1s22s22p63s23p63d104s0. Number of unpaired electrons =0.
Hence, FeH2O62+ has the highest magnetic moment.

ZnH2O62+

Q.41. Explain with two examples each of the following: coordination entity, ligand, coordination number, coordination
polyhedron, homoleptic and heteroleptic.

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Solution: (i) Coordination entity:

It is the radical or species that have a positive or negative charge. The central atom or ion is surrounded by a
number of neutral molecules or negative ions (called ligands). For example:
NiNH362+,FeCN64+= cationic complex
PtCl42-,AgCN2-= anionic complex
NiCO4,CoNH34Cl2= neutral complex.

(ii) Ligands
The neutral molecules or negatively charged ions that surround the metal atom in a coordination entity or a
coordinate complex are known as ligands. They donate a lone pair of electrons. For example, N¨H3,H2O¨,Cl-.

(iii) Coordination number:

The total number of lone pairs donated by ligands (either neutral molecules or negative ions) attached to the
central metal atom in the coordination sphere is called the coordination number of the central metal atom.
For example:
(a) K2PtCl6, six chloride ions attached to Pt in the coordinate sphere. So the coordination number of Pt is 6.
(b) NiNH34Cl2, the coordination number of the central atom Ni is 4.

(iv) Coordination polyhedron:

The spatial arrangement of the ligands attached to the central metal ion directly in the coordination sphere.
For example:
(a)

(b) Tetrahedral

(v) Homoleptic complexes:

The complexes in which the metal ion bonded to only one kind of donor group. For e.g.: CoNH363+,PtCl42-,
etc.
(vi) Heteroleptic complexes:
The complexes in which the central metal ion is bound to more than one type of donor group.
For e.g.: CoNH34Cl2+,CoNH35Cl2+.

Q.42. Amongst the following, the most stable complex is

FeH2O63+FeNH363+FeC2O433-

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Solution: The stability of a complex increases by chelation, the most stable complex is FeC2O433-.

C2O4-2 is a bidentate chelated ligand.

Complex structure is

FeCl63-

Q.43. What will be the correct order for the wavelengths of absorption in the visible region for the following:
NiNO264-, NiNH362+, NiH2O62+

Solution: Since the central metal ion in all the three complexes is the same, the absorption in the visible region depends
on the ligands. The order in which the crystal field splitting energy values of the ligands increases in the
spectrochemical series is as follows:
H2O<NH3<NO2-
Hence, the amount of crystal-field splitting observed will be in the following order:
∆oH2O<∆oNH3<∆oNO2-
Therefore, the wavelengths of absorption in the visible region will be in the order:
NiNO264-<NiNH362+<NiH2O62+

Q.44. What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.

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Solution: (a) Unidentate ligands: The ligands which have only one donor site are called Unidentate ligand. For example,
N¨H3,Cl-, etc.
(b) Didentate ligands: The ligands that have two donor sites are called Didentate ligands.

For example, (1) Ethane-1,2-diamine

(2) Oxalate ion

(c) Ambidentate ligands:

Ligands that can attach themselves to the central metal atom through two different atoms are called ambidentate
ligands. For example:

(The donor atom is N)

(The donor atom is oxygen).

In CN- ligand the donor atom can be carbon or nitrogen.

Q.45. Specify the oxidation number of the metal in the following coordination entity:
CoH2OCNen22+

Solution: CoH2OCNen22+
Let the oxidation number of Co be x.
The charge on the complex is +2.
H2O is a neutral ligand. So, the oxidation number is zero.
CN is negatively charged ligand and oxidation number is -1.
en is neutral ligand so its oxidation number is zero.
CoH2OCNen22+
x+0+-1+20=+2
x-1=+2
x=+3.

Q.46. Specify the oxidation number of the metal in the following coordination entity:

CoBr2en2+

Solution: Br- is negatively charged ligand and its oxidation number is -1.

en is a neutral ligand, so its oxidation number =0

CoBr2en2+x+2-1+20=+1x-2=+1x=+3

Q.47. Specify the oxidation number of the metal in the following coordination entity:

PtCl42-

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Solution: Let the oxidation number of Pt be x

Cl is negatively charged ligand and its oxidation number =-1

The charge on the complex is -2 PtCl42- x+4-1=-2x=+2

Q.48. Specify the oxidation number of the metal in the following coordination entity:

K3FeCN6

Solution: Let the oxidation number of Fe be x

CN is negatively charged ligand and its oxidation number =-1

The oxidation number of K=+1 K3FeCN63+1+x+6-1=0x=+3

Q.49. Specify the oxidation number of the metal in the following coordination entity:

CrNH33Cl3

Solution: Let the oxidation number of Cr be x

Cl is negatively charged ligand and its oxidation number =-1

NH3 is a neutral ligand and its oxidation number=0 [Cr(NH3)3Cl3] x+30+3-1=0x=+3

Q.50. Using IUPAC norms write the formula for the following:
Tetrahydroxozincate(II)

Solution: Tetrahydroxozincate(II) :
The central metal atom is zinc and the oxidation number of Zn=+2.
Hydroxide (OH-) is negatively charged ligand and its oxidation number =-1
Charge on complex =4(-1)+(+2)=x
x=-2 (complex is negatively charged)
Hence, the complex is ZnOH4-2

Q.51. Using IUPAC norms write the formula for the following:
Potassium tetrachloridopalladate(II)

Solution: Potassium tetrachloridopalladateII

Central metal atom is palladium Pd and the oxidation number of Pd =+2

Chloride is negatively charged ligand and its oxidation number=-1 Charge on co-ordination sphere=4-1++2=x
x=-2 Hence, the formula is K2PdCl4.

Q.52. Using IUPAC norms write the formula for the following:
Diamminedichloridoplatinum(II)

Solution: The central metal is platinum (Pt) and the oxidation number of Pt=+2

Chloride is negatively charged ligand and its oxidation number=-1

Ammine NH3 is a neutral ligand and its oxidation number=0 Charge on complex=20+2-1++2=x x=0 Hence, the
formula is PtNH32Cl2.

Q.53. Using IUPAC norms write the formula for the following:
Potassium tetracyanonickelate(II)

Solution: Potassium tetracyanonickelate(II)

The central metal atom is nickel (Ni) and the oxidation number of Ni=+2

Cyano CN- is negatively charged ligand and its oxidation number=-1

Charge on complex=4-1++2x=-2 Potassium has +1 oxidation number so to balance the charge on complex two
potassium ions present in the complex.
Hence, the complex is K2NiCN4

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Q.54. Using IUPAC norms write the formula for the following:
Tetrabromidocuprate(II)

Solution: Tetrabromidocuprate(II) :
The central metal atom is copper Cu and the oxidation number of Cu=+2

Bromide Br- is negatively charged ligand and its oxidation number=-1

Charge on the complex=4-1++2=x x=-2 (Negatively charged complex) Hence, the formula is CuBr42-.

Q.55. Using IUPAC norms write the formula for the following:
Pentaamminenitrito-O-cobalt(III)

Solution: Pentaamminenitrito-O-cobalt(III) :
Central metal atom is cobalt (Co) and the oxidation number of Co=+3

Nitrito-O ONOis negatively charged ligand and its oxidation number=-1

Ammine NH3 is a neutral ligand and its oxidation number=0 Charge on the complex=50+1-1++3=x
x=+2(Complex is positively charged) Hence, the formula is CoONONH352+.

Q.56. Using IUPAC norms write the formula for the following:
Hexaamminecobalt(III) sulphate

Solution: Hexaamminecobalt(III) sulphate :

The central metal atom is cobalt (Co) and the oxidation number of Co=+3

Ammine NH3 is a neutral ligand and its oxidation number =0

Hence, the formula is CoNH362SO43.

Q.57. Using IUPAC norms write the formula for the following:
Potassium tri(oxalato)chromate(III)

Solution: Potassium tri(oxalato)chromate(III)

Central metal atom is chromium (Cr) and the oxidation number of Cr=+3

Oxalate C2O4-2 is negatively charged ligand and its oxidation number=-2

Charge on complex=3-2++3=xx=-3 Potassium has +1 oxidation number. So, to balance the charge on complex
three potassium ions present in complex.
Hence, the complex is K3CrC2O43.

Q.58. Using IUPAC norms write the formula for the following:
Hexaammineplatinum(IV)

Solution: Hexaammineplatinum(IV) :
The central metal atom is platinum (Pt) and the oxidation number of Pt=+4

Ammine NH3 is a neutral ligand and its oxidation number=0

Charge on complex=60+4=x x=+4 Hence, the formula is PtNH364+.

Q.59. Using IUPAC norms write the formula for the following:
Pentaamminenitrito-N-cobalt(III)

Solution: Pentaamminenitrito-N-cobalt(III) :
The central metal atom is cobalt (Co) and the oxidation number of Co=+3

NO2- is negative ligand and its oxidation number=-1

Ammine NH3 is a neutral ligand and its oxidation number=0 Charge on complex=+3+1-1+50=x x=+2 Hence,
the formula is CoNO2NH35+2.

Q.60. Using IUPAC norms write the systematic name of the following:
CoNH36Cl3

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Solution: CoNH36Cl3
Let the oxidation number of Co be x.
NH3 is neutral ligand its name is ammine and its oxidation number =0
The oxidation number of Cl=-1.
The oxidation number of central metal atom =
x+60+3(-1)=0
x=+3
Therefore, the complex is positively charged
So, the name of the compound is Hexaamminecobalt(III) chloride.

Q.61. Using IUPAC norms write the systematic name of the following:

PtNH32ClNH2CH3Cl

Solution: Let the oxidation number of Pt be x

NH3 is a neutral ligand its name is ammine and its oxidation number=0

NH2CH3, a neutral ligand its name is methylamine and its oxidation number=0 Oxidation number of Cl =-1
Oxidation number of central metal atom. x+20+1-1+10=+1x=2 Therefore, the complex is positively charged.
So, the name of the compound is Diamminechlorido(methylamine) platinum(II) chloride.

Q.62. Using IUPAC norms write the systematic name of the following:

TiH2O63+

Solution: Let the oxidation number of Ti be x.

H2O is a neutral ligand, it's name is 'aqua' and it's oxidation number=0

The oxidation number of the central metal atom. ⇒x+60=+3⇒x =+3 The complex is positively charged, So the
name of the compound is Hexaquatitanium(III) ion.

Q.63. Using IUPAC norms write the systematic name of the following:

CoNH34ClNO2Cl

Solution: Let the oxidation number of Co be x.

NH3 is a neutral ligand, its name is ammine and its oxidation number=0

Cl- and NO2- is negatively charged unidentate ligand. Their name is chlorido and nitrito- N (nitrogen is bonded
to the metal atom) respectively and their oxidation number is -1. The oxidation number of central metal atom is
1(x)+40+1-1+1-1+1-1=0x=+3 The complex is positively charged, So the name of the compound is
Tetraamminechloridonitrito-N-Cobalt (III) chloride.

Q.64. Using IUPAC norms write the systematic name of the following:

NiCO4

Solution: Let the oxidation number of Ni be x.

CO is a neutral ligand, its name is carbonyl and its oxidation number=0

The oxidation number of the central metal atom=0 Prefixes mono, di, tri, etc., are used to indicate the number of
the individual ligands in the coordination entity. Oxidation state of the metal in coordination entity is indicated
by Roman numeral in parenthesis. If the complex ion is a neutral, the metal is named same as the element. So,
the name of the compound is Tetracarbonylnickel(0).

Q.65. Using IUPAC norms write the systematic name of the following:

MnH2O62+

Solution: Let the oxidation number of Mn be x.

H2O is a neutral ligand, its name is 'aqua' and its oxidation number =0

The oxidation number of the central metal atom is: 1(x)+60=+2x=+2 The complex is positively charged, So the
name of the compound is Hexaquamanganese(II) ion.

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Q.66. Using IUPAC norms write the systematic name of the following:

NiCl42-

Solution: Let the oxidation number of Ni be x.

Cl- is negatively charged, unidentate ligand, its name is "chlorido" and its oxidation number= -1

The oxidation number of the central metal atom is 1(x)+4-1=-2x=-2+4x=+2 The complex ion is an anion, the
name of the metal ends with the suffix – ate. It contains four chloride ligands. Oxidation state of the metal in
cation, anion or neutral coordination entity is indicated by Roman numeral in parenthesis. So, the name of the
compound is Tetrachloridonickeltate(II) ion.

Q.67. Using IUPAC norms write the systematic name of the following :

NiNH36Cl2

Solution: Let the oxidation number of Ni be x.

NH3 is a neutral, unidentate ligand, its name is ammine and its oxidation number=0

The oxidation number of central metal atom = 1x+60=+2x=+2 Oxidation state of the metal in coordination
entity is indicated by Roman numeral in parenthesis. If the complex ion is a cation, the metal is named same as
the element. In the given compound six ammonia ligands are attached to the central atom and outside the
coordinate entity chloride ions are present. So, the name of the compound is Hexaamminenickel(II) chloride.

Q.68. Using IUPAC norms write the systematic name of the following:

Coen33+

Solution: Let the oxidation number of Co be x.

en is a neutral, bidentate ligand, its name is ethane-1,2-diamine and its oxidation number is zero.

The oxidation number of the central metal atom=+3 Oxidation state of the metal in coordination entity is
indicated by Roman numeral in parenthesis. If the complex ion is a cation, the metal is named same as the
element. When the names of the ligands include a numerical prefix, then the terms, bis, tris, tetrakis are used,
the ligand to which they refer being placed in parentheses. So, the name of the compound is Tris(ethane- 1,2-
diamine)cobalt(III)ion.

Q.69. List various types of isomerism possible for coordination compounds, giving an example of each.

Solution:

(a) Geometric isomerism:

This type of isomerism is common in heteroleptic complexes. It arises due to the different possible geometric
arrangements of the ligands. For example: PtNH32Cl2 When the coordination number is four. The tetrahedral
compounds do not show geometrical isomerism as we all know that all four positions are equivalent in a
tetrahedral geometry. So, moving on to square planar complexes there are different possibilities depending upon
the formula of the compound.

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Another type of geometrical isomerism occurs in octahedral coordination entities of the type Ma3b3 like
[Co(NH3)3 (NO2)3].

If three donor atoms of the same ligands occupy adjacent positions at the corners of an octahedral face, we have
the facial (fac) isomer. When the positions are around the meridian of the octahedron, we get the meridional
(mer) isomer.

(b) Optical isomerism: A Coordination compound which can rotate the plane of polarised light is said to be
optically active. When the coordination compounds have the same formula but differ in their ability to rotate
directions of the plane of polarised light are said to exhibit optical isomerism, and the molecules are optical
isomers. The optical isomers are pair of molecules which are non-super impossible mirror images of each other.
This is due to the absence of elements of symmetry in the complex. This type of isomerism arises in chiral
molecules. Isomers are mirror images of each other and are non-superimposable.

(c) Linkage isomerism: This type of isomerism is found in complexes that contain ambidentate ligands.
For example, CoNO2NH352+has two isomeric forms having red and yellow colours. The red coloured isomer
is CoONONH352+ named as pentaamminenitrito-O-cobalt (III) cation while the yellow isomer is formulated
as CoNO2NH352+. It is named as pentaamminenitrito-N-cobalt (III) cation. In the first cation, we have
Co-(ONO) link, while in the second case, NO2 coordinates to the metal ion through the nitrogen atom,
Co-(NO2).

(d) Coordination isomerism:

This type of isomerism arises when the ligands are interchanged between cationic and anionic entities of
different metal ions present in the complex. For example CoNH36CrCN6 and CrNH36CoCN6
These isomers are expected to have significant differences in their physical and chemical properties.

(e) Ionisation isomerism:

This type of isomerism arises when a counter ion replaces a ligand within the coordinator sphere. Thus,
complexes that have the same composition, but furnish different ions when dissolved in water are called
ionisation isomers. For e.g.,(i) [CoNH35SO4]Br and [CoNH35Br]SO4.

(f) Solvate isomerism:

Solvate isomers differ by whether or not the solvent molecule is directly bonded to the metal ion or merely
present as a free solvent molecule in the crystal lattice.
[CrH2O)6Cl3, violet
CrH2O5ClCl2.H2O, grey-green
CrH2O5Cl2Cl. 2H2O, dark green.

Q.70. How many geometrical isomers are possible in the following coordination entity?
CrC2O433-

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Solution: Geometrical isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the
ligands. But the given coordination entity is homoleptic complex.

For CrC2O433-, geometrical isomers are not possible because C2O42- is a symmetrical bidentate ligand.

Q.71. How many geometrical isomers are possible in the following coordination entity?

CoNH33Cl3

Solution: Two geometrical isomers are possible:

Facial or (fac): Two triangular faces such that each corner is occupied by similar ligands.

Meridional or (mer): If the three ligands and the metal ion are in one plane, the isomer is said to be meridional.

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Intext questions

Q.1. Write the formula for the following coordination compound:

Tetraamminediaquacobalt III chloride

Solution: The complex name is Tetraamminediaquacobalt (III) chloride.

Given ligands: Ammine NH3 – neutral ligand; Aqua H2O-Neutral ligand.
Charge on coordination sphere:

1(+3)+2(0)+4(0)=x

x=+3 The complex is cationic. Following the rules for a cationic coordination complex, we get the formula as:
CoH2O2NH34Cl3.

Q.2. Write the formula for the following coordination compound:

Potassium tetracyanidonickelateII

Solution: Potassium tetracyanidonickelate II:

Given Ligand is cyanide (CN-) and number of ligands are four.

Charge on coordination sphere is =1(+2)+4(-1)=x 2-4=x-2=x Given Complex is anionic

because the coordination sphere carries a negative charge. So the formula of the given molecule is K2NiCN4.

Q.3. Write the formula for the following coordination compound:

Tris(ethane-1,2-diamine) chromium III chloride

Solution: Complex name is Tris(ethane-1,2-diamine) chromium III chloride.

Given ligand is ethylenediamine en. It is neutral and bidentate ligand.

Charge on coordination sphere= x=1(+3)+3(0) x=+3 The complex is

cationic and the formula of the molecule is Cren3Cl3.

Q.4. Write the formula for the following coordination compound:

Amminebromidochloridonitrito-N-platinate II

Solution: The complex name is Amminebromidochloridonitrito-N-platinateII.

Given ligands are ammine-NH3 (neutral), Nitrito-NO2-, Bromido-Br-, Chlorido-Cl-

Charge on coordination sphere is x=1(+2)+1(0)+1(-1)+1(-1)+1(-1) x=2-3x=-1 Nitrogen atom from NO2- is

bonded with the central metal. The complex is anionic, So the formula of the complex is PtNH3BrClNO2-.

Q.5. Write the formula for the following coordination compound:

Dichloridobis(ethane-1,2-diamine)platinum IV nitrate

Solution: The complex name is Dichloridobis(ethane-1,2-diamine)platinumIV nitrate.

Given ligands are ethylene diamineen-neutral ligand and chloridoCl--negative ligand.

Charge on coordination sphere is =1(+4)+2-1+2(0)=x x=+2 The complex is cationic, Charge on coordination
sphere neutralised by nitrate ions NO3-, So the formula of the compound is PtCl2en2NO32.

Q.6. Write the formula for the following coordination compound:

IronIIIhexacyanidoferrateII

Solution: The complex name is IronIIIhexacyanidoferrateII.

Given ligand is cyano-CN-

Charge on coordination sphere is =1(+2)+6-1=x x=-4 The complex is anionic and counter metallic ion has +3
charge. Hence, the formula of the molecule is Fe4FeCN63.

Q.7. The hexaquamanganese (II) ion contains five unpaired electrons, while the hexacyano ion contains only one unpaired
electron. Explain using Crystal Field Theory.
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Solution: Mn(II) has an electronic configuration of 3d54s0. In the case of hexaaquomanganese (II) ion the ligand attached
to metal is water which is a weak field ligand and is not able to pair up the electrons of 3d sub-shell and the
configuration is t2g3 and eg2. Whereas, in the case of hexacyano ion the CN− is a strong field ligand and it
causes pairing of electrons in the d-orbitals and hence there exist only one unpaired electron in t2g5eg0.

Q.8. Write the IUPAC name of the following coordination compound:

CoNH36Cl3

Solution: Let the oxidation number of Central atom Co be "x"

NH3 is a neutral unidentate ligand, its name is "ammine"
Oxidation state of central atom

=1x+60+3-1=0

x-3=0x=+3
It is a cationic complex because the coordination sphere is having positive charge. Hence, IUPAC name is
HexaamminecobaltIII chloride.

Q.9. Write the IUPAC name of the following coordination compound:

CoNH35ClCl2

Solution: CoNH35ClCl2

Let oxidation state of central atom Co be "x"

Given ligand is NH3, its name is "ammine" and it is a neutral ligand. Cl- is named as chlorido. The oxidation
state of the central atom =1(x)+50+1-1+2-1=0 x=+3
This is cationic complex and the name of the compound is pentaamminechloridocobaltIII chloride.

Q.10. Write the IUPAC name of the following coordination compound:

K3[FeCN6]

Solution: The IUPAC names of the coordination compound K3FeCN6:

The central atom is iron.

Ligand CN- name is cyano. Complex type is anionic. Oxidation state of central metal is +3. The complex
should start with cation, here the cation is potassium. Anion is coordination sphere. IUPAC name is potassium
hexacyanoferrateIII.

Q.11. Write the IUPAC name of the following coordination compound:

K3FeC2O43

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Solution: The central atom is Iron.

Ligand is Oxalate ion.

Oxidation state of central metal is +3. The complex should start with cation, here the cation is potassium. Anion
is coordination sphere. While writing the coordination sphere, the ligands should be written in alphabetical
order. IUPAC name is potassium trioxalatoferrateIII.

Q.12. Write the IUPAC names of the following coordination compound

K2PdCl4

Solution: The central atom is Palladium.

Ligand is Chloride.

Complex type is anionic and the oxidation state of cental metal is +2. The complex should start with
cation. Here the cation is potassium and anion is coordination sphere. IUPAC name is potassium
tetrachloridopalladate(II).

Q.13. Write the IUPAC name of the following coordination compound:

PtNH32ClNH2CH3Cl.

Solution: The IUPAC name of the coordination compound PtNH32ClNH2CH3Cl

The central atom is Platinum.

Ligands are NH2CH3methylamine, Cl-chlorido, NH3ammine. The oxidation state of the cental metal is +2.
Complex type is cationic. IUPAC name is diamminechlorido(methylamine)platinum(II) chloride.

Q.14. Indicate the types of isomerism exhibited by the following complex and draw the structures for these isomers
K[CrH2O2C2O42].

Solution: Both cis or trans geometrical isomers for KCrH2O2C2O42 can exist. Also, optical isomers for cis-isomer
exists.

Trans-isomer of the compound is optically inactive. While cis-isomer is optically active.

Q.15. Indicate the types of isomerism exhibited by the following complex and draw the structures for these isomers.

Coen3Cl3

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Solution: Optical isomers are possible for both tetrahedral and octahedral complexes, but not square planar. They are
optical isomers (Enantiomers)-Mirror images which are non-superimposable on each other. Optical Isomers are
isomers which are non-superimposable mirror images.
The given compound has two optical isomers.

Q.16. Indicate the types of isomerism exhibited by the following complex and draw the structures for these isomers

CoNH35NO2NO32.

Solution: The isomerism exhibited by this compound is optical isomerism and linkage isomerism.

A pair of optical isomers:

These are mirror images and non-superimposable. So they are called as Enantiomers.

Due to the presence of ambidentate ligand, it can also show linkage isomerism.

Linkage isomers are CoNH35ONONO32 and CoNH35NO2NO32.

Q.17. Indicate the type of isomerism exhibited by the complex [Pt(NH3)(H2O)Cl2] and draw the structures for its isomers.

Solution: [Pt(NH3)(H2O)Cl2] belongs to the [Mabc2] family of square planar complexes where, a, b and c are the three
ligands attached to the central metal atom or ion M. This complex will exhibit cis-trans geometrical isomerism.

Q.18. Give evidence that CoNH35ClSO4 and CoNH35SO4Cl are ionisation isomers.

Solution: When dissolved in water, they give different ions in solution which can be tested by adding AgNO3 solution
and BaCl2 solution, i.e.,
CoNH35ClSO4+Ba2+→BaSO4(white precipitate)

CoNH35ClSO4+Ag+→No reaction

CoNH35SO4Cl +Ba2+→No precipitate CoNH35SO4Cl+Ag+→AgCl(white precipitate). Hence, these two are

ionisation isomers.

Q.19. Explain on the basis of valence bond theory that NiCN42- ion with square planar structure is diamagnetic and the NiCl42-
ion with tetrahedral geometry is paramagnetic.

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Solution: In NiCN42-, Ni is in the +2 oxidation state, i.e., in d8 configuration.

d8 configuration:

There are four CN- ions. It either has a tetrahedral geometry or square planar geometry. CN- ion is strong field
ligand, the pairing of unpaired 3d electrons take place.

It now undergoes dsp2 hybridisation. Since all electrons are paired, it is diamagnetic.

In the case of NiCl42-,Cl- ion is a weak field ligand. Therefore, it does not lead to the pairing of unpaired 3d
electrons. Therefore, it undergoes sp3 hybridisation.

Since there are two unpaired electrons, in this case, it is paramagnetic in nature.

Q.20. NiCl42- is paramagnetic while NiCO4 is diamagnetic though both are tetrahedral. Why?

Solution: Although NiCl42- and NiCO4 are both tetrahedral, their magnetic characters are different. This is because of
the difference in the nature of ligands. Cl- is a weak field ligand and it does not cause the pairing of unpaired 3d
electrons. Hence, NiCl42- is paramagnetic.

In NiCO4,Ni is in the zero oxidation state i.e., it has a configuration of 3d84s2.

But CO is a strong field ligand. Therefore, it causes the pairing of unpaired 3d electrons. Also, it causes the 4s
electrons to shift to the 3d orbital, thereby giving rise to sp3 hybridisation. Since no unpaired electrons are
present in this case, NiCO4 is diamagnetic.

Q.21. FeH2O63+ is strongly paramagnetic whereas, FeCN63- is weakly paramagnetic. Explain.

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Solution: In both FeH2O63+ and FeCN63-, Fe exists in the +3 oxidation state i.e., in d5 configuration.

CN- is a strong field ligand. So the pairing of unpaired electrons takes place. So, only one unpaired electron left
in d-orbital.

Therefore,
μ=nn+2
=11+2
=3
=1.732 BM
On the other hand, H2O is a weak field ligand. Therefore, it cannot cause the pairing of electrons. So,
the unpaired electrons are 5.
Therefore,
μ=nn+2
=55+2
=35
≅6 BM
Thus, it is evident that FeH2O63+ is strongly paramagnetic, while FeCN63- is weakly paramagnetic.

Q.22. Explain CoNH363+ is an inner orbital complex whereas NiNH362+ is an outer orbital complex.

Solution: In CoNH363+ the oxidation state of Co is +3. So its configuration is Ar3d64s0. Since, NH3 is a strong field
ligand it causes the electrons to pair up and thus results in an inner orbital complex formation having
hybridisation as d2sp3. On the other hand, in NiNH362+, Ni is in +2 oxidation state having configuration
of Ar3d84s0. Even though NH3 is a strong ligand and might cause pairing, then only one free d-orbital is left
and therefore it forms an outer orbital complex having the sp3d2 hybridisation.

Q.23. Predict the number of unpaired electrons in the square planar PtCN42- ion.

Solution: PtCN42-
In this complex, Pt is in +2 oxidation state. It forms a square planar structure and it undergoes dsp2
hybridisation. Now, the electronic configuration of Pt+2 is 5d8.

CN- is a strong field ligand, so, there will be pairing of unpaired electrons. All electrons get paired, so, no
unpaired electrons present in PtCN42-.

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 Isomerism in Coordination Chemistry
(Chapter 20 H&S)

Isomers
Compounds with same formula
but different atom arrangement

Structural Isomers Stereoisomers

Compounds with different Compounds with same connectivity
connections between atoms but different spatial arrangement

Linkage isomers
Same ligand connected Diastereomers
by different atoms (Geometric isomers)
Non-mirror images OR
Ionization isomers
Give different ions different coordination
in solution polyhedra

Polymerization isomers
Same empirical formula
but different molar mass
Optical isomers
Coordination isomers (Enantiomers)
Different ligand sets in Mirror image isomers
complex cation and anion
Hydration isomers
Contain different
numbers of waters
inner/outer sphere
Structural Isomerism
Linkage isomers: same ligand connected by different atoms

Ionization isomers: different ions when dissolved

exchange of ions between inner and outer coordination sphere

eg. [Co(NH3)5Br][SO4] vs. [Co(NH3)5(SO4)]Br

Methods to distinguish these?

Polymerization isomers: identical empirical formulae but different
molar masses (i.e. different degrees of aggregation)

Coordination isomers: found in special cases where both the

cation and anion are complexes

egs. [Co(NH3)6][Cr(CN)6] vs. [Cr(NH3)6][Co(CN)6]

[Pt(NH3)4][PtCl6] vs. [Pt(NH3)4Cl2][PtCl4]

Hydration isomers: exchange of water and another ligand between

inner and outer coordination sphere

eg. [Cr(H2O)4Cl2]Cl·2H2O (green crystals from c. HCl soln)

→ (dissolve H2O) [Cr(H2O)5Cl]Cl2·H2O (blue-green)

→ (heat) [Cr(H2O)6]Cl3 (violet)

Stereoisomerism

Diastereoisomers (geometrical isomers): essentially includes all

isomers that have the same M-L connectivity but a different spatial
arrangement of donors AND are not mirror image isomers

Note: this wider definition includes what are often termed ‘geometrical’ isomers such
as cis/trans complex and complexes of different polyhedral arrangements (eg. sq.
pyramidal vs. TBP). While strictly correct, some prefer to reserve the term
‘diastereomers’ for optical isomers that are NOT enantiomers (i.e. in the same way it
is used in organic chemistry: eg. RR and RS are diastereomers but not enantiomers)

CN 4
Square planar: ML2X2 type

cis and trans isomers

CN 5 (isomers defined below often interconvert)

TBP: MXL4 and MX2L3

MXL4 M M

MX2L3 M M M

SqPyr: MXL4 and MX2L3

MXL4 M M

MX2L3 M M M
CN 6
Oh: all vertices identical so only one structure for MXL5

MX2L4 M M

MX3L3 M M M
Optical isomers (enantiomers): only includes isomers that are
optically active (rotate plane-polarized light) and mirror images

Special case in Oh metal complexes:

helical chirality of tris(chelates)

eg. Co(acac)3

mirror
plane

M M
 Distortions in Octahedral Geometry
L

L L
M
L L

L
Regular Octahedron: Complexes with regular octahedral geometry are expected to
form, when all of the ligands are of the same kind

Distorted Octahedron: Complexes

C l with
ith distorted
di t t d octahedral
t h d l geometry
t are expected
t d to
t
form, when the ligands are of different kinds
 Distortions in Octahedral Geometry
If the
th ground d electronic
l t i configuration
fi ti off a non-linear
li complex
l isi orbitally
bit ll
degenerate, the complex will distort so as to remove the degeneracy and
achieve a lower energy. This is called the Jahn-Teller Effect

d8 d9

eg eg

t2g t2g

Ni2+: Only one way of Cu2+: Two ways of filling the eg orbitals;
filling the orbitals; not there is degeneracy and Jahn-Teller
degenerate and no Jahn- Distortion is observed
Teller Distortion
 Jahn-Teller Distortion in Cu(II) Complexes

dx2-y2

eg
energy
dz2

dxy
t2g

Cu(II) in regular octa- dxz dyz

hedral environment [C F6]4-
[CuF
Cu(II) after J-T distortion
Jahn-Teller Distortion in d9 Complexes

Δo >> δ1 > δ2.

 Jahn-Teller Distortion in d1 Complexes

dz2
eg
energy
dx2-yy2

dxz dyz
t2g

d1 in regular octa- dxy

hedral environment
d1 after J-T distortion
 d1 Vs d9

d9 d1

Distortions are more pronounced if the degeneracy occurs in an eg orbital

 Distortions in Low-Spin Complexes

× × ×

×
Distortions in High-Spin Complexes

× ×

× ×
 Thermodynamic Aspects of CFSE

Lattice Energy: Estimated using Borne-Lande equation

Heats of hydration for M2+ ions

 Site Preference in Spinels
M IIAlIII2O4
S i l – Mg
Spinel
AIIBIII2O4

The oxide
Th id ions
i f
form a close
l packed
k d arrangement with
i h octahedral
h d l andd tetrahedral
h d l voids
id
and the metal ions occupy the voids.

Normal Spinels: (AII)tet(BIII2)octO4

The divalent AII ions occupy the tetrahedral voids, whereas the trivalent BIII ions
occupy the octahedral voids in a close packed arrangement of oxide ions.
MgAl2O4, Mn3O4, ZnFe2O4, FeCr2O4

Inverse Spinels: (BIII)tet(AIIBIII)octO4

The AII ions occupy the octahedral voids, whereas half of BIII ions occupy the
tetrahedral voids.
F 3O4, CoFe
Fe C F 2O4, NiFe
NiF 2O4
 Site Preference in Spinels

NiFe2O4

Ni is in +2 oxidation state and has 8 electrons in the d orbitals

In a tetrahedral void,
Configuration – e4t24; CFSE – 0.8 Δt (0.4 Δo)
In an octahedral void,
Configuration – t2g6eg2; CFSE – 1.2 Δo
Fe is in +3 oxidation state and has 5 electrons in the d orbitals
In a tetrahedral void,
void
Configuration – e2t23; CFSE – 0
In an octahedral void,
Configuration – t2gg3eg2; CFSE – 0

Hence, it is advantageous to have Ni2+ ion in the octahedral voids. This results in an
inverse spinel structure for the compound.
FeIII[NiIIFe
F F III]O4
 Site Preference in Spinels

Mn3O4

When Mn is in +2 oxidation state, it has 5 electrons in the d orbitals

In a tetrahedral void,
Configuration – e2t23; CFSE – 0
In an octahedral void,
Configuration – t2g3eg2; CFSE – 0
When Mn is in +3 oxidation state, it has 4 electrons in the d orbitals
In a tetrahedral void,
void
Configuration – e2t22; CFSE – 0.4 Δt (0.2 Δo)
In an octahedral void,
Configuration – t2gg3eg1; CFSE – 0.6 Δo

Hence, it is advantageous to have Mn3+ ions in the octahedral voids. This results in a
normal spinel structure for the compound.
MnII[MnIII]2O4
 Origin of Color

The Beer-Lambert Law

A = logg10((Io/I)) = εcl
where ε is the molar extinction coefficient ( in L cm-1 mole-1 ), c is concentration in mole L-1
and l is the path length in cm. A is known as ‘Absorbance’ and it is dimensionless.
 Color of [Ti(H2O)6]3+

Absorption
Ab i at 520 nm
gives the complex its
purple color

A more resolved absorption spectrum of the complex has a shoulder

Color and CFT
 Color and CFT

[Cr(NH3)6]3+ [Cr(NH3)5Cl]2+

Strong ligands,
ligands leading to Relatively weak set of ligands,
ligands
high Δo. Absorbs violet leading to reduced Δo. Absorbs
and appears yellow. yellow and appears magenta.
 Laporte Rule

In a molecule or ion possessing center of symmetry, transitions are not allowed

between orbitals of same parity. Transitions are only possible between orbitals that
differ byy Δl = ±1;; ‘l’ is the orbital qquantum number.

Examples of forbidden transitions are: s to s, d to d, p to f etc.

Tetrahedral geometry is not affected by this rule as it does not have a center of
symmetry.
As a consequence, ε for tetrahedral complexes are 100 times more than the ε for
octahedral complexes.
comple es

Even octahedral complexes lose their center of symmetry transiently due to

unsymmetrical vibrations. This leads to color in octahedral and square planar
complexes
 Spin-forbidden and Spin-allowed Transitions

Any transition for which ΔS¹≠0 is strongly forbidden; that is, in order to be allowed, a
transition must involve no change in spin state.

Allowed Forbidden

[Mn(H2O)6]2+ has a d5 metal ion and is a high-spin complex. Electronic transitions are
not only Laporte-forbidden, but also spin-forbidden. The dilute solutions of Mn2+
complexes are therefore colorless.
colorless
However, certain complexes such as MnO4-, CrO42- etc are intensely colored even
though they have metal ions without electrons in the d orbitals. The color of these
complexes are not from dd-dd transitions,
transitions but from charge
charge-transfer
transfer from ligand to metal
orbitals.
 d0 and d10 ions have no d-d transitions

Zn2+ d10 ion white

TiF4 d0 ion white
TiCl4 d0 ion white
TiBr4 d0 ion orange
TiI4 d0 ion dark brown

[M O4]‐ Mn(VII)
[MnO M (VII) d0 ion
i extremely
t l purple
l
[Cr2O7]‐ Cr(VI) d0 ion bright orange

[Cu(MeCN)4]+ Cu(I) d10 ion colourless

[Cu(phen)2]+ Cu(I) d10 ion dark orange
 Substitution in Octahedral Metal Complexes
(continued)

We have seen that substitution kinetics are influenced by the metal

in ID mechanisms:

 d count effects (Jahn-Teller effects, ΔCFSE)

 metal ion charge
 2nd and 3rd row effects (slower substitution due to increased
M-L bond strength and larger ΔCFSE)

But what about ligand effects?

1) Entering vs. leaving group effects in an ID mechanism

 entering group shouldn’t matter much (post rate step)

[Ni(H2O)6]2+ + L → [Ni(H2O)5(L)]n+ + H2O

L log k

F- 3.9
SCN- 3.8
CH3CO2- 4.3
NH3 3.5
H2O 4.4
 Leaving groups should have a large effect:

k1 for [Co(NH3)5(H2O)]3+ + X- → [Co(NH3)5(X)]2+ + H2O

k-1 for [Co(NH3)5(X)]2+ + H2O → [Co(NH3)5(H2O)]3+ + X-

K for [Co(NH3)5(H2O)]3+ + X- [Co(NH3)5(X)]2+ + H2O

X k-1 (s-1) K = k1/k-1 (M-1)

NCS- 5.0 x 10-10 470

F- 8.6 x 10-8 20
H2PO4- 2.6 x 10-7 7.4
Cl- 1.7 x 10-6 1.25
Br- 6.3 x 10-6 0.37
I- 8.3 x 10-6 0.16
NO3- 2.7 x 10-5 0.077

k1 is the rate of water loss and this is a constant (ca. 10-6 or 10-7 s-1)

 K gives a measure of the ground state bond strengths for

complexes with X- relative to water (K = k1/k-1)

 k-1 gives a measure of the rate of water displacing X-

(aquation)
Since the M-X bond is breaking in the transition state of
aquation in an ID mechanism it SHOULD reflect the strength
of that bond, as does the equilibrium constant K: a plot of
log K vs. log k-1 should therefore be linear (a linear free
energy relationship, LFER):
2) Effects of spectator (ancillary) ligands on ID rates

a) transition state is 5-coordinate square pyramidal: metal

suffers a loss of electron density relative to the ground state

How will the electron donating or withdrawing properties of the

ancillary ligands affect the rate of substitution of another ligand?

 better σ- and π-donors will stabilize (lower the energy of)

the transition state, increasing the rate of reaction

 π-acceptors will destabilize the transition state and slow

the reaction down

[NiL5X]+ + H2O → [NiL5(H2O)]2+ + X-

rate for L = NH3 >> L = H2O; NH3 is a better σ-donor

b) size effects: bigger ligands destabilize higher coordination

numbers (i.e. ground state) relative to smaller coordination
numbers (i.e. transition state)

cis-[Mo(CO)4(L)2] + CO → [Mo(CO)5L] + L

L = PPh3 > Ph2PMe > PhPMe2

Other indicators of reaction mechanism

things already mentioned indirectly...

 rate laws, order of reaction and sensitivity of rates to

identity of the incoming ligand

1) entropy of activation, ΔS‡

Eyring equation (a theoretical derivation from transition state

theory) allows determination of ΔH‡ and ΔS‡ by measurement of
the T dependence of the rate constant:

ln(k/T) = -ΔH‡/RT + ΔS‡/R

plot ln(k/T) vs. 1/T gives a straight line of slope -ΔH‡/R and
intercept ΔS‡/R where T is in K and R is the gas constant
(8.3144 J mol-1 K-1)

eg. Ln(allox)3 (Allox is a 2

bidentate N,O chelate)
1
undergoing isomerization by
a Ray-Dutt twist 0
ln (k/T)

-1
‡ -1
ΔH = 24 kJ mol -2
slope = -2850
intercept = 11.8

ΔS‡ = +99 J mol-1 K-1

-3

0.0035 0.0040 0.0045 0.0050

-1
1/T (K )
  negative entropy of activation implies a more ordered
(and presumably associative) transition state

 positive entropy of activation implies a less ordered (and

presumably dissociative) transition state

But careful...

 errors in ΔS‡ are typically very large

 changes in entropy could be due to other effects
(differential solvation of the ground and transition state)

2) volume of activation, ΔV‡

From the pressure dependence of the equilibrium constant:

(∂lnk/∂P)T = -ΔV‡/RT OR ΔV‡ = -RT(∂lnk/∂P)T

so the negative of the slope of a lnk vs. P plot gives ΔV‡

ΔV‡ can tell us about volume changes going to the

transition state:

 positive volume changes imply ID (or D) mechanisms

 negative volume changes imply IA (or A) mechanisms

[M(H2O)6]2+ d count rate ΔV‡ mechanism

V d3 87 -4.1 IA
Mn d5 hs 2.1 x 107 -5.4 IA

Fe d6 hs 4.4 x 106 3.8 ID

Co d7 hs 3.2 x 106 6.1 ID
Ni d8 3.2 x 104 7.2 ID
COURSE
GUIDE

CHM 423
COORDINATION CHEMISTRY

Course Team Prof. O. S. Lawal (Developer/Writer) --

NOUN
Prof. Olayinka O. Ajani (Course Reviewer)
Department of Chemistry
Covenant University, OTA

NATIONAL OPEN UNIVERSITY OF NIGERIA

CHM 423 COURSE GUIDE

© 2021 by NOUN Press

National Open University of Nigeria
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University Village
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URL: www.nou.edu.ng

All rights reserved. No part of this book may be reproduced, in any form
or by any means, without permission in writing from the publisher.

Printed 2021

ISBN: 978-978-058-082-7

ii
CHM 423 COURSE GUIDE

CONTENTS PAGE

Introduction......................................................................... iv
What You Will Learn in this Course……………………… iv
Course Aims......................................................................... v
Course Objectives................................................................ v
Working through this Course............................................... vi
Course Materials…………………………………………… vi
Study Units........................................................................... vii
Textbooks and References………………………………… vii
Assessment........................................................................... viii
Course Overview…………………………………………… viii
How to Get the Most from this Course…………………….. viii
Summary…………………………………………………… ix
Table of Contents…………………………………………… ix

iii
CHM 423 COURSE GUIDE

INTRODUCTION

Coordination Chemistry involves the study of coordination compounds,

their structures, properties and applications. The term ‘Coordination’ is
used to describe compounds that stems from the nature of chemical bond.
This chemical bond called coordinate covalent bond involves donation of
electron pair(s) by a molecule or negatively charged ion, a Lewis base, to
a neutral metal or positively charged ion, a Lewis acid. These compounds
are known, from spectroscopic studies, to exist in various structures based
on the number of ligands i.e. Lewis base that coordinates to the metal.

The unique ability of the coordination compounds to exist in diverse

shapes provides them to exhibit properties which make them to be useful
in living systems (e.g. Haemoglobin, an important biological molecule in
transportation of oxygen), medicine (e.g. Cisplatin, used in treatment of
cancer) and in industries (e.g. Petroleum Industry where a number of
coordination compounds are used as catalysts involved in chemical
processes such as hydrogenation, aromatisation etc).

Many coordination compounds have been in use before their

classification and characterisation; for example Prussian blue [Fe(CN)6]3-
, a coordination compound, has been used for decades in textile industry
as a pigment before the chemistry of coordination compounds began
historically with Alfred Werner (1866-1919). The contributions of Alfred
Werner to coordination chemistry served as the foundation upon which
other chemists built to explain the nature, structures, properties and
application of these compounds.

WHAT YOU WILL LEARN IN THIS COURSE

Coordination chemistry provides the information on the mode of action

of biological molecules based on their structural studies. With such
knowledge, scientists have been able to design and modify several
important biological molecules. This course will expose you to the
applications of previous knowledge acquired in spectroscopic techniques,
chemical kinetics, thermodynamics and reaction mechanisms. The course
will open a new world to students with interest in medicine, where
knowledge of coordination chemistry is employed in the extraction of
metal poison in living systems, and petrochemical industry, where the
knowledge of coordination chemistry is important in catalyst design and
application.

In coordination chemistry, you will acquire knowledge on the

nomenclature, preparation, classification, stereochemistry, bonding,
reaction kinetics and mechanisms, chemical equilibrium and
thermodynamics of reactions of metal complexes. Also, in this course,

iv
CHM 423 COURSE GUIDE

you are expected to know how various spectroscopic techniques (such as

absorption and vibrational spectroscopy) and other physical methods
(such as magnetic properties) are employed in characterisation of metal
complexes.

COURSE AIMS

The aims of this course are to:

 introduce the chemistry of coordination compounds (definition,

recognition, preparation and application)
 provide you with knowledge on how to; name coordination
compounds using IUPAC system of naming (nomenclature),
 classify coordination compounds based on their coordination
numbers (coordination formula) and identify number and types of
various isomers possible with each coordination compound
(isomerism)
 identify various structures and hybridisation(s) possible with each
coordination compound based on its coordination number
(stereochemistry)
 expose you to the physical methods (magnetic properties,
vibrational and electronic spectroscopy) used in structural analysis
of coordination compounds
 explain the various bonding theories (valence bond theory, crystal
field theory, ligand field theory and molecular orbital theory) and
modifications resulting into spectrochemical series (due to trend
observed in crystal field splitting) and nephelauxetic series (due to
trend observed in cloud expansion)
 explain how complex formation can assist in stabilisation of
unusual oxidation states
 provide details of reaction kinetics and mechanisms,
thermodynamics and stability constants as well as chelate
formation and effect.

COURSE OBJECTIVES

In order to achieve the aims set out above, the course sets overall
objectives. In addition, each unit also has specific objectives. The unit
objectives are always given at the beginning of a unit; you should read
them before you start working through the unit. You may also want to
refer to them during your study of the unit so as to check on your progress.
You should always look at the unit objectives after completing a unit. In
this way, you can be sure that you have done what was required of you by
the unit.

v
CHM 423 COURSE GUIDE

Below are the wider objectives of the course, as a whole. By meeting these
objectives, you should have achieved the aims of the course as a whole.
On successful completion of the course, you should be able to:

 identify coordination compounds, explain the methods used in

preparing them and state areas of their applications
 name, classify and identify the possible number of isomers of any
given coordination compound.
 describe the structures and hybridisations of coordination
compounds
 apply physical techniques in characterisation of coordination
compounds
 explain the nature of bonding in coordination compounds through
the various bonding theories
 apply the knowledge of coordination chemistry in stabilisation of
unusual oxidation states
 describe various types of reaction mechanism, kinetics and
thermodynamics possible in coordination chemistry.

WORKING THROUGH THIS COURSE

The course content of CHM 423 (Coordination Chemistry) is presented

in four (4) modules subdivided into various units. A list of textbooks is
provided at the end of each module for further reading. Each unit contains
SAQs and ITQs. At certain points in the course you would be required to
submit assignments for grading and recording purposes. You are also to
participate in the final examination at the end of the course. Each unit
ends with worked examples and assignments to enable students have
better understanding and perform excellently in this course. Having
provided this much information on this course, it is expected that you
should study the course material in details, organise and attend tutorial
classes.

COURSE MATERIALS

The major components of the course include the following:

1. Course Guide
2. Study Units
3. In-Text Questions
4. Self-Assessment Questions
5. Conclusion
6. Summary
7. Assignment File
8. Textbooks and References

vi
CHM 423 COURSE GUIDE

STUDY UNITS

This course consists of the following study units grouped into four
modules.

Module 1

Unit 1 Introduction to Coordination Chemistry

Unit 2 Nomenclature and Coordination Number of Complexes
Unit 3 Isomerism in Complexes
Unit 4 Preparation and Reactions of Complexes

Module 2

Unit 1 Theories of Structure and Bonding

Module 3

Unit 1 Physical Methods of Structural Investigation

Module 4

Unit 1 Thermodynamic Stability and Reaction Kinetic of

Complexes

TEXTBOOKS AND REFERENCES

Textbooks suggested for further reading are listed below. Some of these
textbooks can be found online and in the libraries. In addition, related
information is also available on the internet but you should identify and
study information relevant to the Course.

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rded.). Inter-Science Publishers, a Division of John Wiley and
Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E.& Sharpe, A. G. (2005). Inorganic Chemistry (2nded.).

Pearson Education Limited.

vii
CHM 423 COURSE GUIDE

Miessler, G. L. &Tarr, D. A.(2010).Inorganic Chemistry.(3rded.).Pearson

Education Int.

Primer (2019). Coordination Chemistry. Available online at:

https://sitesmedia.s3.amazonaws.com/chem/files/2013/01/Coordi
nation_chemistry_Primer.pdf.

ASSESSMENT

There are two aspects to the assessment of the course. First are the Tutor-
Marked Assignments (TMA) and there is a written examination. It is
essential that you attempt all exercises and assignments and submit
appropriately to the course facilitator for grading. You are advised to be
sincere in attempting the exercises. In attempting the assignments, you are
expected to apply the information, knowledge and techniques gathered
during the course.

The TMAs shall constitute the continuous assessment component of the

course and it shall constitute 30% of the total course score. You will be
given a number of TMAs to answer. You may do yourself good by reading
and researching well before you attempt to answer the questions. Nearly
all of them must be answered before you are allowed to sit for the end of
the course examination. The end of course examination shall constitute
70% of the total course score.

FINAL EXAMINATION AND GRADING

The end of the course examination for Inorganic Chemistry III will be for
about 3 hours with maximum score of 70% of the total course work. The
examination will be made up of questions which normally reflect on what
you have learnt in the course materials/further reading. In addition, these
questions may be prototype of the self-assessment questions and the
TMAs or not. The end of the course examination is intended to cover the
whole course.

COURSE OVERVIEW

In all, this course is presented in four (4) modules.

Module 1 contains introduction to coordination chemistry, IUPAC system
of naming complexes, Alfred Werner’s contribution to coordination
chemistry, coordination number and isomerism in complexes. This
module explains the fundamentals of coordination chemistry.

Module 2 explains the bonding schemes (Valence Bond Theory, Crystal

Field Theory, Adjusted Crystal Field theory and Molecular Orbital
theory) used to

viii
CHM 423 COURSE GUIDE

describe the nature of bonding in metal complexes and the limitation(s)

of each scheme leading to its modification to account for certain
properties of metal complexes.

Module 3 describes the electronic and vibrational properties of bonds in

metal complexes through which the structural elucidation of complexes
can be made with the aid of electronic and vibrational spectroscopic
methods. It also explains the magnetic nature of complexes, which also
provides information on the structure of metal complexes.

Module 4 provides information on the kinetics (rate of reaction of metal

complexes), thermodynamic and stability constant (i.e. equilibrium). It
also provides information on unique stability associated with Chelate
formation.

HOW TO GET THE MOST FROM THIS COURSE

In order to obtain an excellent grade in this course, you must study each
unit of the course in details and carefully practice the worked examples at
the end of each unit. You should also take advantage of group discussion
and tutorials to solve the assignment at the end of each unit. In doing so,
you will be able to compare your understanding of the course contents
with your colleagues. Each unit contains SAQs and ITQs. At certain
points in the course you would be required to submit assignments for
grading and recording purposes. You are also to participate in the final
examination at the end of the course.

SUMMARY

CHM 423 (Coordination Chemistry) explains the concept of formation of

metal complexes, their nomenclature, characterization and applications.
The course includes review of crystal field theory, crystal field
stabilisation energies: origin and effects on structures and thermodynamic
properties. Also included in the course are introduction to absorption
(electronic states of partly filled quantum levels, selection rules for
electronic transitions, splitting of the free ion energy levels in octahedral
and tetrahedral complexes, Orgel and Tanabe-Sugano diagrams) and
vibrational spectroscopy and magnetism (magnetic susceptibilities
transition metal complexes, effect of orbital contributions arising from
ground and excited states, deviation from the spin-only approximation).

ix
 MAIN
COURSE

CONTENTS PAGE

Module 1……………………………………………………… 1

Unit 1 Introduction to Coordination Chemistry………… 1

Unit 2 Nomenclature and Coordination Number of
Complexes……………………………………….. 10
Unit 3 Isomerism in Complexes………………………… 18
Unit 4 Preparation and Reactions of Complexes………… 27

Module 2………………………………………………………… 33

Unit 1 Theories of Structure and Bonding………………… 33

Module 3…………………………………………………………. 49

Unit 1 Physical Methods of Structural Investigation……… 49

Module 4…………………………………………………………. 81

Unit 1 Thermodynamic Stability and Reaction Kinetic

of Complexes………………………………………. 81
CHM 423 MODULE 1

MODULE 1

Unit 1 Introduction to Coordination Chemistry

Unit 2 Nomenclature and Coordination Number of Complexes
Unit 3 Isomerism in Complexes
Unit 4 Preparation and Reaction of Complexes

UNIT1 INTRODUCTION TO COORDINATION

CHEMISTRY

CONTENTS

1.0 Introduction
2.0 Intended Learning Outcomes
3.0 Main Content
3.1 Definition and Recognition of Coordination Compounds
(Complexes)
3.2 Werner’s Contributions to Coordination Chemistry
3.2.1 Electrolyte and Non-Electrolyte Complexes
3.3 Ligands
3.4 Application and Importance of Coordination Compounds
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

Coordination chemistry is the foundation of modern inorganic and

bioinorganic chemistry, both of which have contributed immensely to the
development of the chemical industry and medicine. The knowledge of
coordination chemistry has provided insight into the mode of actions
(kinetics and mechanisms) of biological molecules in living systems.
Important biological molecules such as vitamin B12, chlorophyll,
haemoglobin and myoglobin are coordination compounds of cobalt,
magnesium and iron respectively. The comprehensive understanding of
the mode of actions of these complex molecules has been made possible
through the knowledge of coordination chemistry. Coordination
chemistry has also contributed to the growth of textile industry where
dyeing involves the use of coordination compounds. The tremendous
growth in the petrochemical industry would not have been made possible
without catalysts design which requires the knowledge of coordination
chemistry. From this background, the knowledge of coordination
chemistry is inevitable to chemists if not all scientists.

1
CHM 423 COORDINATION CHEMISTRY

2.0 OBJECTIVES

By the end of this unit, you should be able to:

 define and recognise coordination compounds or complexes

 explain Werner’s contributions and distinguish between primary
and secondary valencies in complexes
 differentiate between electrolyte and non-electrolyte complexes
 recognise different types of ligands
 state the difference between homoleptic and heteroleptic
complexes
 state areas of application of coordination compounds.

3.0 MAIN CONTENT

3.1 Definition and Recognition of Coordination Compounds

(Complexes)

Complexes or coordination compounds are molecules that possess a metal

center that is bound to ligands (atoms, ions, or molecules that donate
electrons to the metal). These complexes can be neutral or charged. When
the complex is charged, it is stabilized by neighboring counter-ions.

Coordination compounds are formed by the reaction between Lewis acids

and Lewis bases. By definition, Lewis acids are electron pair acceptors
while Lewis bases are electron pair donors. Thus, a Lewis acid must have
empty suitable orbitals to accommodate the donated electron pairs. The
presence of empty suitable orbitals in transition metals (Cu, Co, Fe etc)
and some compounds (BF3, BeCl2 with empty p-orbital) and ions (H+) of
main block elements makes them to act as Lewis acids. However, the
chemistry of coordination compounds is restricted to compounds in which
the Lewis acid is a transition metal or d-block elements.

A molecule can function as a Lewis base provided it has heteroatom(s)

with lone pair(s) on them. Examples of such molecules are H2O, NH3 and
CO. Anions such as halides (F-, Cl- and Br-), cyanide (CN-) are also Lewis
bases. The chemical interaction between a Lewis acid and a Lewis base
results in coordinate bond formation; hence, the product of the interaction
is called coordination compound.

By definition, coordination compound is compound formed when a

central metal atom or ion is surrounded (coordinated) to a number of
anions or molecules in such a way that the number of the coordinated
anions or molecules exceeds the normal covalency of the central atom or
ion. The compound is also referred to as complex because on ionisation,

2
CHM 423 MODULE 1

it exists as an independent species without dissociation, unlike normal or

double salt which dissociates on ionisation. Complexes are enclosed in
square brackets to distinguish them from other types of salts.

Coordination Compounds (Complexes)

Complex Central Anion/molecule Number Valence
Atom/Ion coordinated of the
metal
[Ni(CO)4] Ni CO 4 0

[Fe(CN)6]3- Fe3+ CN- 6 +3

[Ag(NH3)2]+ Ag+ NH3 2 +1

[Co(NH3)4Cl2]+ Co3+ NH3 and Cl- 6 +3

[Cu(H2O)6]2+ Cu2+ H2 O 6 +2

3.2 Werner’s Contributions to Coordination Chemistry

Coordination chemistry emerged from the work of Alfred Werner, a

Swiss chemist who examined different compounds composed of
cobalt(III) chloride and ammonia. Upon the addition of hydrochloric acid,
Werner observed that ammonia could not be completely removed. He
then proposed that the ammonia must be bound more tightly to the central
cobalt ion. However, when aqueous silver nitrate was added, one of the
products formed was solid silver chloride. The amount of silver chloride
formed was related to the number of ammonia molecules bound to the
cobalt(III) chloride. For example, when silver nitrate was added to
CoCl3·6NH3, all three chlorides were converted to silver chloride.

However, when silver nitrate was added to CoCl3·5NH3, only 2 of the 3

chlorides formed silver chloride. When CoCl3·4NH3 was treated with
silver nitrate, one of the three chlorides precipitated as silver chloride. The
resulting observations suggested the formation of complex or
coordination compounds. In the inner coordination sphere, which is also
referred to in some texts as the first sphere, ligands are directly bound to

3
CHM 423 COORDINATION CHEMISTRY

the central metal. In the outer coordination sphere, sometimes referred

to as the second sphere, other ions are attached to the complex ion.

Alfred Werner (1866-1919) became the first Swiss Chemist to receive the
Nobel Prize in Chemistry due to his contribution to coordination
chemistry. He prepared, characterised and studied both physical and
chemical properties of some coordination compounds by simple
experimental techniques such as precipitation. From his findings, he made
the following conclusions:

i. Central metal atom or ion in a complex possesses two kinds of

valencies named primary and secondary valencies.
ii. The primary valency is ionisable and can be satisfied by anions
only. It can be considered as the oxidation state of the central
metal.
iii. The secondary valency is not ionisable and can be satisfied by both
molecules and anions. It gives rise to the coordination number.
iv. The spatial arrangement of the anions and molecules satisfying the
secondary valency determines the shape of the complex.

The complex species is enclosed in square bracket while the anions

satisfying only the primary valency lie outside the coordination sphere
(square bracket). Note that anions in the coordination sphere satisfied both
primary and secondary valencies but the molecules only satisfy secondary
valency.

From Werner’s postulates geometries have been assigned to complexes

based on the number of the secondary valencies.

Complex, Primary and Secondary Valencies, Possible Shape

Complex Primary Secondary Possible

Valency valency Shape
[Ni(CO)4] 0 4 Tetrahedral or square planar

K4[Fe(CN)6] +2 6 Octahedral

[Ag(NH3)2]Cl +1 2 Linear

[Co(NH3)4Cl2]Cl +3 6 Octahedral

[Cu(H2O)6]2+ +2 6 Octahedral

4
CHM 423 MODULE 1

3.2.1 Electrolyte and Non-Electrolyte Complexes

By precipitation of chloride ions (Cl-) using silver nitrate (AgNO3)

solution on complexes of cobalt with similar chemical composition
(CoNH3Cl3), Werner was able to distinguish two different kind of
complexes which he classified as non-electrolytes and electrolytes.

From his experiment, a complex containing chloride(s) which gave

precipitate on reacting with AgNO3 solution was said to be an electrolyte,
while non-electrolyte gave no precipitate. The precipitated chloride
satisfied only primary valency, i.e. it was outside the coordination sphere
while un-precipitated chloride satisfied both primary and secondary
valencies, i.e. it was in the coordination sphere.

With improvement in technology, complexes containing other forms of

anions can now be classified as electrolyte or non-electrolyte by
measuring their electrical conductivity. It is worthy to note that for
complexes with net negative charge ([Fe(CN)6]4-), cations can balance out
charge resulting to electrolyte complexes (K4[Fe(CN)6]). Therefore, a
complex is said to be an electrolyte if it has counter ion (cation or anion)
outside coordination sphere while a complex with zero net charge is called
non-electrolytes because no counter ion will be present.

Electrolyte and Non-Electrolyte Complexes

Complex Colour Mole of Cl- Class Electrolyte
precipitated Ratio
[Co(NH3)6]Cl3 Yellow 3 Electrolyte 1:3

[Co(NH3)5Cl]Cl2 Purple 2 Electrolyte 1:2

Trans- Green 1 Electrolyte 1:1

[Co(NH3)4Cl2]Cl

Cis- Violet 1 Electrolyte 1:1

[Co(NH3)4Cl2]Cl

[Co(NH3)3Cl3] 0 Non- -
Electrolyte

3.3 Ligands

Ligands are Lewis bases which coordinate to central metal atom or ion in
a complex. They may be molecules with heteroatom (e.g. H2O, NH3,
PPH3 etc) having lone pair(s), anions (e.g. CN-, F-, Cl-, SCN-), unsaturated
hydrocarbons (H2C=CH2, C4H4), aromatics(C6H6) or macromolecules
like proteins, vitamins, porphyrin etc.

5
CHM 423 COORDINATION CHEMISTRY

Ligands can be group into different classes based on the number of donor
atoms (sites) they possess. A ligand with one donor site is called
monodentate (e.g. H2O, NH3, CN-, Cl-). Bidentate ligands are those with
two binding sites e.g. ethylenediamine (H2NCH2CH2NH2), oxalate
(C2O4)2- etc. These ligands are capable of forming ring structure (Chelate)
with central metal. Tridentate ligands possess three donor atoms e.g.
diethylenetriamine (H2NCH2CH2NHCH2CH2NH2). They have the
capacity to form two ring structures around the central metal. Ligands
with four donor sites are said to be quadridentate e.g.
(H2NCH2CH2NHCH2CH2NHCH2CH2NH2) triethylene tetraamine, they
are capable of forming complexes with four ring structures. Polydentate
ligands have many donor sites e.g. ethylenediaminetetra acetate (EDTA).
Another category of ligands are called ambidentate ligands because they
have two heteroatoms and any can be used to coordinate to metal
depending on the reaction conditions e.g. SCN- (it can either coordinate
through S or N), NO2- (it can coordinate through O or N).

Structures of Ligands

3.4 Application and Importance of Coordination Compounds

i. Inorganic Analysis
Coordination compounds are employed in quantitative and
qualitative analyses of metals. The presence of metal can be
detected by using aqueous ammonia to form complex of the metal
if present. An example is the deep blue colour given by aqueous
solution of Cu2+ on addition of ammonia solution. Estimation of
the quantity of a metal e.g. Cu2+, Zn2+, Ni2+etc can be carried out
using EDTA solution in the presence of a suitable indicator. This
can be used to quantify the hardness of a given water sample
caused by Ca2+ and Mg2+.

ii. Purification of Metals

Metals such as Gold and Nickel can be purified by complexation
reaction. Gold in a given sample can be complexed with CN- to
give [Au(CN)2]-. By reacting the complex with Zn, the Gold can
be recovered in a pure state. Also, Nickel purification involves

6
CHM 423 MODULE 1

formation of [Ni(CO)4] from a given impure sample. The complex

can be easily decomposed to obtain pure Nickel.

Pure titanium metal is made by chlorination of the oxide TiO2 to

form the tetrahedral complex TiCl4. This is then reduced in a redox
reaction with magnesium metal to yield free titanium metal as a
powder. To provide a continuous loop of reagents, the MgCl2 also
formed in this reduction step is electrolysed to produce chlorine
and magnesium metal. With the chlorine and magnesium re-used
fully, this is a good example of an industrial process with little
environmental pollution.

iii. Industry
In the petrochemical industry, Nickel, Platinum and Rhodium
complexes are used as catalyst in hydrogenation reaction, Cobalt
and rhodium complexes are used in hydroformylation (conversion
of alkene to aldehyde) reaction. EDTA is used in production of
cream, food etc as preservative to trap any metal that may cause
discoloration of the products. Brilliant and intense colours of many
complexes make them of great value as dyes and pigments.
Examples are copper phthalocyanine and Prussian blue.

iv. Medicine
In medicine, metal poison, such as Lead poison, can be treated by
the use of ligands like EDTA as sequestering agent to form
harmless complex with the toxic metal. Major breakthrough has
been reported in the use of Cis-Platin, [PtCl2(NH3)2] and other
related drugs in cancer treatments. Technetium complexes are used
in imaging of internal organ in living organisms. Auranofin (gold
complex) is used in treatment of arthritis. Budotitane and
titanocene dichloride (anticancer drugs) are titanium complexes.

v. Important Biological Complexes

Photosynthesis is made possible in green plant due to the presence
of Magnesium complex chlorophyll used to trap the required light
energy. Iron complex called Haemoglobin helps in transportation
of Oxygen within the body while Myoglobin another Iron complex
helps to store Oxygen.

These are some of the areas where complexes play important role in our
lives.

7
CHM 423 COORDINATION CHEMISTRY

SELF-ASSESSMENT EXERCISE

i. The chemistry of coordination compounds is restricted to

compounds in which the Lewis acid is a …………… element
ii. What are the primary and secondary valencies of [Co(NH3)4Cl2]Cl
?
iii. What is possible shape of the [Cu(H2O)6]2+ according to Werner's
postulation

4.0 CONCLUSION

The chemistry of coordination compounds is an important aspect of

modern inorganic chemistry. It helps in transformation of many industries
and explains the ways in which biological molecules function in living
systems. Many of these transformations are made possible due to the
contributions of Alfred Werner and other notable Scientists to
coordination chemistry.

5.0 SUMMARY

Werner’s contribution provided information on the unique characteristics

of coordination compounds. From his findings, it was concluded that
complexes possessed two kinds of valencies called primary and secondary
valencies. The primary valency is only satisfied by anions but both
molecules and anions can satisfy the secondary valency which influences
the geometry of the complex unlike primary valency.

The anions and molecules are called ligands which can be monodentate,
bidentate, tridentate, quadridentate or polydentate depending on the
number of available donor sites. The multidentate have capacity to form
multiple rings around the central metal.

6.0 TUTOR-MARKED ASSIGNMENT

1. Based on the number of moles of chlorides precipitated with

AgNO3 solution in the complexes below, assign secondary
valencies to the metals and write the composition of each complex
in square bracket (Time allowed: 10 mins)

2. List and draw the structures of five (5) examples of each of the
following types of ligands
i. Monodentate ligands
ii. Bidentate ligands
iii. Tridentate ligands
iv. Polydentate ligands
v. Ambidentate ligands (Time allowed: 10 mins)

8
CHM 423 MODULE 1

3. Write the Chemical formula of five complexes used in cancer

treatment. (Time allowed: 5 mins)
4. Classify the underlisted complex as either first or second sphere:
K3[Fe(SCN)6]; CoCl3.6NH3 ; PdCl2.4NH3 (Time allowed: 6 mins)

7.0 REFERENCES/FURTHER READING

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rd ed.). Interscience Publishers, a Division of John Wiley and
Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry (2nd ed.).

Pearson Education Limited.

Miessler, G. L. & Tarr, D. A. (2010). Inorganic Chemistry (3rd ed.).

Pearson Education Int.

LibreText (2019). Introduction to Coordination Chemistry. Anushweta

Asthana (Contributor). Updated June 5, 2019. Available online at:
https://chem.libretexts.org/Bookshelves/Inorganic_Chemistry/Su
pplemental_Modules_(Inorganic_Chemistry)/Coordination_Che
mistry/Structure_and_Nomenclature_of_Coordination_Compoun
ds/Introduction_to_Coordination_Chemistry

9
CHM 423 COORDINATION CHEMISTRY

UNIT 2 NOMENCLATURE AND COORDINATION

NUMBER OF COMPLEXES

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 IUPAC System of Naming Metal Complexes
3.2 Coordination Number of Metal Complexes
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

Nomenclature in coordination chemistry has undergone several

modifications. While some of the old and trivial names are still in use for
some complexes, International Union of Pure and Applied Chemistry
(IUPAC) provides the modern and most acceptable system of naming
complexes. The IUPAC naming system put into consideration the nature
of the complex whether cationic or anionic, the number and nature of the
ligands as well as the bonding mode (bridging and non-bridging mode)
adopted by the ligand. It is worthy to note that isomeric complexes can
also be identified from their nomenclature. The IUPAC naming system
has many features that make it unique and widely acceptable.

2.0 OBJECTIVES

By the end of this unit, you should be able to:

 name metal complexes

 identify coordination number of metal complexes
 state possible geometry associated with a given coordination
number.

3.0 MAIN CONTENT

3.1 IUPAC System of Naming Metal Complexes

Many coordination compounds have very complex structures due to the

nature of their ligands. This may give rise to their name being long and
complicated. With IUPAC system of naming, the complication in naming

10
CHM 423 MODULE 1

is not removed but the naming process is organised in a way that it can be
easily comprehended by anybody who understand the rules behind it.

Rules for Naming Complexes

The following rules must be observed in naming complexes:
Rule 1: For negative complex the positive counter ion (cation) is named
first if present, followed by the complex. This is the common way of
naming simple salts as well e.g. NaCl Sodium Chloride. For positive
complex, the complex is named first before naming the negative counter
ion (anion).

Examples:
Complex Name
K2[Ni(CN)4] Potassium tetracyanonickelate(II)
[Co(NH3)6]Cl3 Hexamminecobalt(III)chloride

Rule 2:In the coordination sphere, the ligands are named before the metal
in alphabetical order of the ligands’ names; however, the metal ion is
written first in formula. The coordination sphere is enclosed in square
brackets in the formula.

Examples:
Complex Name
[Cu(NH3)4(H2O)2]SO4 Tetraamminediaquacopper(II) sulphate
[Co(NH3)5Cl]Cl2 Pentaamminechlorocobalt(III) chloride

Rule 3: The number of ligands in a complex is indicated by one or both

of the prefixes listed below. If the name of the ligand contains the first
prefix or is complicated, it is enclosed in parenthesis and the second set
of prefix is used. Examples below will show how these prefixes are used.

Number First prefix Second prefix

2 Di Bis
3 Tri Tris
4 Tetra Tetrakis
5 Penta Pentakis
6 Hexa Hexakis
7 Hepta Heptakis
8 Octa Octakis
9 Nona Nonakis
10 Deca Decakis

Complex Name
[Co(H2NCH2CH2NH2)2Cl2]Cl Dichlorobis(ethylenediammine)cobalt
(III) chloride

11
CHM 423 COORDINATION CHEMISTRY

[Fe(NH4C5-C5H4N)3]Cl2 tris(bipyridine)iron(III) chloride

Rule 4: Anionic ligands e.g. Br-, Cl-, F-, SO42-etc are named with a suffix
“o” while neutral ligands retained their usual name except H2O called
aqua, NH3 called ammine. Note also that the name of the metal in an
anionic complex ends with a suffix “ate”

Ligand Name Metal

Name in
anionic complex
Br- (Bromide) Bromo Copper
Cuprate
2-
SO4 (Sulphate) Sulphato Iron Ferrate
C2O42- (Oxalate) Oxalato Nickel Nickelate
CN- (Cyanide) Cyano Platinum
Platinate
-
-SCN (Thiocyanate) Thiocyanato-S Titanium
Titanate
-
SCN-(Isothiocyanate) Thiocyanato-N Gold
Aurate

Complex Name
K4[Fe(SCN)6] Potassium hexathiocyanatoferrate(II)
[Ni(C2O4)2]2- bis(oxalato)nickelate(II)
[Ti(C2O4)2] bis(oxalato)titanium(IV)
K[Au(CN)2] Potassium dicyanoaurate(i)

Rule 5: For complexes with geometric isomers, these isomers are

indicated using prefix “cis” and “trans”. For example [PtCl2(NH3)2]

Rule 6: A bridging ligand (a ligand joining two or more metal centers) is

indicated with a prefix “μ” and a subscript to indicate the number of the
metal centers bridged by the ligand. Examples

12
CHM 423 MODULE 1

μ2-amido-μ2-hydroxobis(pentaamminecobalt (III)) cation

bis(tetraaqua-μ2-hydroxo iron (II)) cation

3.2 Coordination Number of Metal Complexes

The coordination number of a metal ion in a complex is the number of

ligand donor atoms to which the metal is directly bonded. It is determined
by counting the number of the donor atoms or site directly attached to the
metal. The ions or molecules that bind to transition-metal ions to form
these complexes are called ligands (from Latin, "to tie or bind"). The
number of ligands bound to the transition metal ion is called the
coordination number. Coordination number varies from 1 to 8, though the
two extremes are rare. The structure of a ligand strongly depends on the
coordination number as it determines the number of spatial orientation
possible in any given complex.

Coordination compounds, such as the FeCl4– ion and CrCl3 6NH3, are
called such because they contain ions or molecules linked, or coordinated,
to a transition metal. They are also known as complex ions or coordination
complexes because they are Lewis acid-base complexes. Although,
coordination complexes are particularly important in the chemistry of the
transition metals, some main group elements also form complexes.
Aluminum, tin, and lead, for example, form complexes such as the AlF63-
, SnCl42– and PbI42– ions. The various coordination numbers will be
considered and the possible structures discussed.

Coordination Number1: complexes having coordination number 1are

rare and little is known of their chemistry.

Coordination Number 2: The complex with coordination number 2 well

established are silver complexes e.g. [Ag(NH3)2]+ where the electronic
configuration of Ag + is d10. The hybridisation of Ag+ is sp with bond angle
1800 and the possible shape is linear structure. Other examples are
[Hg(CN)2], [Au(CN)2] etc.
[H3N→Ag←NH3]+. The arrows point from the donors to the acceptor.

13
CHM 423 COORDINATION CHEMISTRY

Coordination Number 3: Complexes with coordination number 3 are

few. Metals with d10 configuration are commonly found with this
coordination number. The hybridisation is sp2 bond angle 1200, which
gives rise to trigonal planar structure. [HgI3]-, [AuCl(PPh3)2],
[Au(PPh3)3]+ etc. Coordination number 3 is favoured by bulky ligand that
can induce steric hindrance and prevent further coordination.

Coordination Number 4: This is a common coordination system which

can give rise to two different geometries i.e. Tetrahedral and square
planar, depending on the orbital of the central metal that received the
donor pairs. Divalent ions such as Zn2+, Cd2+, Hg2+and Cu+ with d10
electronic configuration and zero crystal field stabilisation energy will
give rise to tetrahedral complexes with sp3hybridisation with bond angle
1090 examples [CdCl4]2-, [Zn(OH)4]2-and [Hg(Br)4]2-.Similarly, few
metals with d0 and d5 are known to form tetrahedral complexes MnO4-,
MnCl42-,TiCl4. Metals with other d-configurations have very limited
number of tetrahedral complexes e.g. [NiCl42-] and [Ni(CO)4]with d8
configuration.

Square Planar Complexes are common with metals d8 electronic

configuration. Examples are [PtCl2(NH3)2], [Ni(CN)4]2- and PdCl42-. The
hybridisation in these complexes is dsp2 with bond angle of 900.

14
CHM 423 MODULE 1

Coordination Number 5: Two possible structures with coordination

number 5 are square based pyramidal and trigonal bipyramidal with the
metal having sp3d hybridisation. In square planar, dx2-y2 orbital in the
metal will receive one of the donated pairs while in trigonal bipyramidal,
dz2 orbital of the metal will receive one of the donated pairs. The energy
difference between the two configurations is small hence they are
interconvertible. Examples are [Fe(CO)5] and [Cu(bipy)2I]+, [VO(acac)2]
and [VO(SCN)4]2-.

Coordination Number 6: This is the most common coordination number

with two possible geometries i.e. octahedral and trigonal prismatic.
Octahedral is the most common with metal centre having sp3d2 or d2sp3
hybridisation with bond angle 900. Examples [Cu(H2O)6]2+, [Co(en)3]3+
and [Fe(CN)6]3-.

OH2 2+
OH2 NC 3-
H2O CN
NC
Cu
Fe
H2O OH2
NC CN
OH2
NC

Higher coordination numbers are possible but not common e.g.

coordination 7[ZrF7]3-and [HfF7]3-, coordination number 8 [ZrF8]4- and
[Mo(CN)8]4-.

SELF-ASSESSMENT EXERCISE

i. Write the formulas for Sodium monochloropentacyanoferrate (III)

ii. Briefly explain how to determine coordination number
iii. Square based pyramidal and trigonal bipyramidal are
interconvertible, why?
iv. According to the IUPAC system of nomenclature for complexes,
what is named before naming the negative counter ion?

15
CHM 423 COORDINATION CHEMISTRY

4.0 CONCLUSION

Nomenclature in coordination chemistry may be complicated but the rules

stated by IUPAC provide a way of having a well-organized and neatly
structured naming system that is widely embraced. Another important
aspect of coordination chemistry apart from nomenclature is the
coordination number which influences the possible geometries complexes
can adopt. From coordination number, the shape, bond angle and
hybridisation of a complex can be predicted.

5.0 SUMMARY

In this unit, you learnt that:

 Coordination compounds can be named with IUPAC system of

naming.
 Coordination number can be used to predict the shape, bond angle
and hybridisation of complexes.
 Coordination numbers 1, 2, 3, 7, 8, 9 and 10 are not as common as
coordination numbers 4, 5 and 6.

6.0 TUTOR-MARKED ASSIGNMENT

1. Write the formulas for the following coordination compounds and

predict possible shape(s), hybridisation(s) and bond angle(s) of
each:

(i) Tetraamminediaquacobalt(III)chloride
(ii) Potassiumtetracyanonickelate(II)
(iii) Tris(ethylenediamine)chromium(III)chloride
(iv) Iron(III) hexacyanoferrate(II)
(v) Hexaammineiron(III) nitrate (Time allowed: 7½ mins)

2 Write the IUPAC names of the following coordination compounds

and predict possible shape(s), hybridisation(s) and bond angle(s)
of each:

(i) [Co(NH3)6]Cl3
(ii) [Co(NH3)5Cl]Cl2
(iii) K3[Fe(CN)6]
(iv) K3[Fe(C2O4)3]
(v) K2[PdCl4] (Time allowed: 5 mins)

16
CHM 423 MODULE 1

7.0 REFERENCES/FURTHER READING

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rd ed.). Interscience Publishers, a Division of John Wiley and
Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry (2nd

ed.).Pearson Education Limited.

Miessler, G. L. & Tarr, D. A. (2010). Inorganic Chemistry (3rd ed.).

Pearson Education Int.

http://www.chemistry.wustl.edu/~edudev/LabTutorials/naming_coord_c
omp.html

Video Tutor on Calculation of Coordination number and nomenclature

https://www.youtube.com/watch?v=r4H5XjJPn58

17
CHM 423 COORDINATION CHEMISTRY

UNIT 3 ISOMERISM IN COMPLEXES

CONTENTS

1.0 Introduction
2.0 Intended Learning Outcomes
3.0 Main Content
3.1 Isomerism
3.1.1 Structural Isomerism
3.1.2 Stereoisomerism
3.2 In-Text Questions and Answers
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

Just as an infinite number of ways exist to arrange large number of

different coloured shoes, there exists different ways on the molecular
scale in which a given number of ligands can be arranged in three-
dimensional array round a central metal. This is the basic concept of
isomerism in coordination chemistry. Different coordination numbers,
shapes and points of attachment of ligands provide an almost infinite
number of three-dimensional structurally related complexes generally
called isomers. Isomerism does not exist in complexes with identical
monodentate and common donor atom ligands. However, wherever more
than one type of ligand is bound, and even where either one type of ligand
with a set of more donor atoms than required, or a number of identical
chelating ligands bind, the possibility of isomerism needs to be
considered. It is important to note that the number of isomers increases
with increase in coordination. The concept of isomerism is well developed
in complexes with coordination numbers 4 and 6 while no established
cases of isomerism is associated with coordination numbers 1, 2 and 3.
The concept of isomerism is very important in drug design as different
isomers have certain differences in reactivity, especially optical isomers.
For instance, an anticancer drug, Budotitane (Titanium complex), lost its
market value when it was discovered to possess optical isomers. This is
because only one isomer may be effective in the treatment of cancer and
the other isomer may cause damaging effect. This underscores the need
to understand the concept of isomerism.

18
CHM 423 MODULE 1

2.0 OBJECTIVES

By the end of this unit, you should be able to:

 define isomerism in coordination chemistry

 differentiate between structural isomerism and stereoisomerism
 identify different structural isomers of a given complex
 differentiate between geometric and optical stereoisomerism.

3.0 MAIN CONTENT

3.1 Isomerism

The existence of coordination compounds with the same formula but

different arrangements of the ligands were crucial in the development of
coordination chemistry. Two or more compounds with the same formula
but different arrangements of the atoms are called isomers. Because
isomers usually have different physical and chemical properties, it is
important to know which isomer we are dealing with if more than one
isomer is possible. Isomerism is a phenomenon used to describe
complexes with the same molecular weight and molecular formula but
different structural and/or spatial arrangement of donor atoms around the
central metal in the coordination sphere. These complexes are called
isomers.

In coordination chemistry, isomers are of different kinds, they include

hydrate or solvent isomers, ionisation isomers, and coordination isomers
having the same overall formula but with different donor atoms of the
same or different ligands attached to the central metal atom or ion. The
nomenclature of different kinds of isomerism is an indication of whether
solvent, anions, or other coordination compounds imposes the isomerism
in the structure. The terms linkage (ambidentate) isomerism is used when
ambidentate ligands impose structural differences in complexes due to use
of different donor atoms on a ligand. Stereoisomers have the same ligands
with the same donor atoms, but differ in the geometric or (spatial)
arrangement of the ligands. Some stereoisomers are optically active
hence, they are classified as optical isomers.

Isomerism in coordination chemistry is divided into structural isomerism

and stereoisomerism. Structural isomers differ in the way ligands or donor
atoms of ligands are arranged round a central metal. Stereoisomers differ
in the spatial arrangement of ligands round the central metal. The figure
below shows different forms of isomerism.

19
CHM 423 COORDINATION CHEMISTRY

3.1.1 Structural Isomerism

Isomers that contain the same number of atoms of each kind but differ in
which atoms are bonded to one another are called structural isomers,
which differ in structure or bond type. Structural isomers are also known
as constitutional isomers, structural isomers have the same empirical
formula but differ in the arrangement of their constituent atoms. This
results in difference in physical properties such as colour. Many different
kinds of structural isomerism occur in coordination chemistry and some
of them will be discussed.

i. Ionisation Isomerism
Ionisation isomers give different ions in aqueous solution. This is
because different anions coordinated to the metal in the
coordination sphere. The isomeric pairs differ in that there is an
exchange of two anionic groups within and outside the
coordination sphere. Ionization isomers occur when a ligand that
is bound to the metal center exchanges places with an anion or
neutral molecule that was originally outside the coordination
complex.

Examples; [Co(NH3)5Br]SO4 (violet) and [Co(NH3)5SO4]Br (red).

Note that in [Co(NH3)5Br]SO4, the sulphate is the counter ion and
can be detected by treating the solution of the complex with BaCl2
to precipitate the sulphate in the form of BaSO4 (qualitative test for
sulphate). The bromide ion is coordinated and will not precipitate
with silver nitrate because it is not free.

20
CHM 423 MODULE 1

In [Co(NH3)5SO4]Br, the test for bromide will be positive since Br-

is not coordinated to the metal while the test for sulphate will be
negative since the sulphate is in the coordination sphere and not
free.

[Pt(en)2Cl2]Br2 and [Pt(en)2Br2]Cl2

[Cr(NH3)4ClBr]NO2 and [Cr(NH3)4ClNO2]Br
[Cr(NH3)5Cl]NO2 and [Cr(NH3)5NO2]Cl
[Co(NH3)4Br2]Cl and [Co(NH3)4ClBr]Br

The difference between the ionization isomers can be view within

the context of the ions generated when each are dissolved in
solution. For example, when pentaammine bromocobalt(II)
chloride is dissolved in water, Cl− ions are generated:

CoBr(NH3)5Cl(s) → CoBr(NH3)+5(aq)+ Cl−(aq)

whereas when pentaammine chlorocobalt(II) bromide is dissolved,

Br− ions are generated:

CoCl(NH3)5Br(s)→ CoCl(NH3)+5(aq)+ Br−(aq)

ii. Hydrate Isomerism

As many complexes are prepared in aqueous solutions where water
is abundant, complexes can precipitate or crystallise with water of
crystallisation outside the coordination sphere or with coordinated
water (ligand) inside the coordination sphere. There are many
isomers which differ in the position of water molecules in their
formula. For example, there are three known hydrate isomers of
CrCl3(H2O)6: [Cr(H2O)6]Cl3 (violet), [Cr(H2O)5Cl]Cl2.H2O (pale
green) and [Cr(H2O)4Cl2]Cl.2H2O (dark green).

The isomers can be distinguished by the mole of silver chloride

precipitated by using silver nitrate on molar solution of the
isomers. In [Cr(H2O)6]Cl3, 3 mole of silver chloride will be
precipitated indicating that none of the Cl- ion is in the
coordination sphere, 2 moles will be precipitated in
[Cr(H2O)5Cl]Cl2.H2O and 1 mole in [Cr(H2O)4Cl2]Cl.2H2O
indicating the number of Cl- not coordinated to the metal ion. The
water of crystallisation outside the coordination sphere can be
detected on dehydration of the complexes.

Other examples are:

[Co(NH3)4(H2O)Cl]Cl2 and [Co(NH3)4Cl2]Cl.H2O
[Co(NH3)5(H2O)](NO3)3 and
[Co(NH3)(NO3)](NO3)2.H2O

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CHM 423 COORDINATION CHEMISTRY

iii. Coordination Isomerism

These isomers contain pairs of ionic complexes that exchange
ligands with each other. Many isomeric pairs are possible by
redistribution of ligands between two metal centres. Examples are:

[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]

[Co(NH3)5(CN)][Cr(CN)5(NH3)] and
[Cr(NH3)5(CN)][Co(CN)5(NH3)]
[Co(en)3][Cr(CN)6] and [Cr(en)3][Co(CN)6]
[Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]
Note that the cationic complex is written first.

A very similar type of isomerism results from replacement of a

coordinated group by a solvent molecule (Solvate Isomerism),
which in the case of water is called Hydrate Isomerism.

A compound with associated water of crystallization is known as

a hydrate. The structure of hydrates can be quite elaborate, because
of the existence of hydrogen bonds that define polymeric
structures.

iv. Linkage Isomerism

This type of isomerism is observed in complexes containing
ambidentate ligands which can coordinate through at least two
different binding sites. Example of such ligand is nitrite (NO2-)
which can coordinate through nitrogen or oxygen.

[Co(NH3)5(NO2)]2+(red) and [Co(NH3)5(ONO)]2+

(yellow)
The yellow complex, [Co(NH3)5(ONO)]2+, is unstable and it is
converted into [Co(NH3)5(NO2)]2+ both in solution and the solid
state either by heating or by exposure to ultraviolet light. The two
isomers can be distinguished through Infrared spectroscopy, for
the O-bonded ligand, characteristic absorption bands at 1065 and

22
CHM 423 MODULE 1

1470 cm-1 are observed, while for the N-bonded ligand, the
corresponding vibrational wave numbers are 1310 and 1430 cm-1.
Other examples are [Co(CN)5(SCN)]3-and[Co(CN)(NCS)]3-,
where the sulphur and nitrogen of the thiocyanate ligand imposes
the observed linkage isomerism.

v. Polymerisation Isomerism
Polymerisation isomers are isomers with the same simplest unit
called monomer. The combination of two or more monomer units
results in polymeric complex isomer. An example is the unit
[Pt(NH3)2Cl2] which on combination can give; [Pt(NH3)4][PtCl4],
[Pt(NH3)3Cl]2[PtCl4] and [Pt(NH3)4][Pt(NH3)Cl3]2. Also the unit
[Co(NH3)3Cl3] on combination will produce [Co(NH3)6][CoCl6],
[Co(NH3)4Cl2][Co(NH3)2Cl4] and [Co(NH3)5Cl][Co(NH3)Cl5].

vi. Ligand Isomerism

This is a form of isomerism due to the isomeric nature of the
ligands. Typical examples are [Pt(NH2CH2CH2CH2NH2)2]2+ and
[Pt(NH2CH(CH3)CH2NH2)2]2+
The ligand propane-1,3-diamine and its isomer,
methylethylenediamine impose the isomerism.

3.1.2 Stereoisomerism

Stereoisomerism occurs in complexes due to difference in spatial

arrangement of ligands round the central metal. Stereoisomerism is
divided into geometric and optical isomerism.

Geometric Isomerism
The most common type of geometrical isomerism involves cis and trans
isomers in square planar and octahedral complexes. In square planar
complex [Pt(NH3)Cl2], the cis- and trans- isomers are shown below. Note
that in the trans-form, identical ligands are separated by bond angle of
1800 while in cis-form the bond angle between identical ligands is 900.

In octahedral complex [Co(NH3)4Cl2]+,cis- and trans- isomers occur

while in [Co(NH3)3Cl3], facial and meridional isomers occur. These are
shown below.

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CHM 423 COORDINATION CHEMISTRY

Optical Isomerism
Optical isomers exist in complexes that are not superimposable on their
mirror images. These isomers have ability to rotate the plane of polarised
light in opposite direction. A mixture of optical isomers of the same
quantity will not rotate the plane of polarised light because the effect of
one isomer is cancelled out by the other. Such a mixture is called racemic
mixture. Optical isomerism is possible in tetrahedral and octahedral
complexes (cis-isomers) where centre of symmetry is absent but not in
square planar complexes. Optical isomers are called enantiomers. A
solution of enantiomer that rotates the plane of polarised light in
clockwise direction is designated as positive (+) or dextrorotatory
(d)enantiomer while the isomer that rotates the plane of polarised light in
anticlockwise direction is designated as negative (-) or laevorotatory (l)
enantiomer. Example is dichlorobis(ethylenediammine)cobalt (III). The
optical isomers have identical chemical and physical properties but differ
in their ability to rotate the plane of polarised light unlike diastereoisomer
that differ in both chemical and physical properties and lacks ability to
rotate the plane of polarised light.

24
CHM 423 MODULE 1

SELF-ASSESSMENT EXERCISE

i. The number of isomers increases with ________ in coordination

ii. Which of the following coordination number has established
isomerism
iii. Chemical tests used to distinguish between [Co(NH3)5Br]SO4 and
[Co(NH3)5SO4]Br require the following reagents except?
iv. Draw the structure of the facial and meridional isomeric form of
[Co(NH3)3Cl3]
v. Using budotitane, explain importance of isomerism concept.
vi. When does ionization isomerism occur?

4.0 CONCLUSION

Isomerism in coordination chemistry provides information on why

complexes with the same chemical formula differ in physical and
chemical properties, and why some complexes with the same formula,
physical and chemical properties differ in their ability to rotate plane
polarised light.

5.0 SUMMARY

You learnt the following in this unit:

 Isomerism are grouped into structural (constitutional) and

stereoisomerism
 Structural isomerism include: Ionisation, Coordination, Linkage,
Hydrate, Polymerisation and Ligand isomerism
 Stereoisomerism is grouped into optical isomerism and geometric
isomerism
 Geometric isomerism is possible in square planar and octahedral
complexes
 Optical isomerism is possible in tetrahedral and octahedral (cis-
isomer) with no centre of symmetry complexes.

6.0 TUTOR-MARKED ASSIGNMENT

1. Only one compound having the formula [Zn(py)2Cl2] (where ‘py’
is pyridine) is known, but two different compounds (isomers) are
known with composition [Pt(py)2Cl2]. Explain these observations
(Time allowed: 5 mins).

2. Write the formulae of polymerisation isomers of [Pd(NH3)2Cl2]

(Time allowed: 3 mins).

3. Give formulae for compounds that are coordination isomers of the

salt [Co(bpy)3][Fe(CN)6]. (Time allowed: 3 mins).

25
CHM 423 COORDINATION CHEMISTRY

7.0 REFERENCES/FURTHER READING

Cotton, F. A., Wilkinson, G., Murillo, C. A., & Bochmann, M. (1999).

Advanced Inorganic Chemistry (6th ed.). New York: Wiley.

DeKock, R. L. & Gray, H. B. (1980). Chemical Structure and Bonding.

Benjamin/Cummings, Menlo Park, CA.

Greenwood, N. N. & Earnshaw, A. (1997). Chemistry of the Elements

(2nd ed.). Oxford, UK.:Butterworth-Heinemann.

Huheey, J. E., Keiter, E. A., &Keiter, R. L. (1993). Inorganic Chemistry:

Principles of Structure and Reactivity (4th ed.). New York: Harper
Collins College Publishers.

Kettle, S. F. A. (1998). Physical Inorganic Chemistry: A Coordination

Approach. New York: Oxford University Press.

Priyanka J. (2019). Isomerism in coordination compounds. A video link

Available at
https://www.youtube.com/watch?v=xOdmRgYAUJQ

26
CHM 423 MODULE 1

UNIT 4 PREPARATION AND REACTIONS OF

COMPLEXES

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Preparation and Reactions of Complexes
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

Many methods are used in the preparation of coordination complexes and

in the transformation of one coordination complex into another. The
preparation and reactions of complexes have generated great research
outputs in synthetic inorganic chemistry. Complexes preparation may
involve; substitution reaction (replacing one or more ligands with others
in a complex), direct reaction (involving only ligand and metal salt
without solvent provided the ligand is a liquid or gas), decomposition
reaction (where a complex is transformed to another by heating at specific
temperature) and redox reaction (where change in oxidation state of the
metal may lead to formation of a new complexes). Redox reaction is
otherwise called ligand electron transfer reaction. There are two different
mechanisms of electron transfer redox reactions: inner sphere or outer
sphere electron transfer. In electron transfer, an electron moves from one
atom to another, changing the charge on each but leaving the net charge
of the system the same. Apart from the various methods stated, a change
in reaction conditions such as pH, temperature, solvent polarity can lead
to formation of new complex. It is, therefore, important to study the
various ways which complexes can be synthesised.

2.0 OBJECTIVES

By the end of this unit, you should be able to:

 explain methods of preparing metal complexes.

 identify type of reactions in metal complexes

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CHM 423 COORDINATION CHEMISTRY

3.0 MAIN CONTENT

3.1 Preparation and Reactions of Complexes

For over two hundred years, coordination complexes have been produced
by a variety of techniques. Among the first few complexes synthesised,
Zeise’s salt, K[Pt(C2H4)Cl3], known for decades, and Werner’s cobalt
complexes serve as template for synthesis of numerous complexes known
today. Synthetic techniques used to prepare coordination complexes range
from simply mixing of reactants to variation of reaction’s conditions and
use of non-aqueous solvents. The methods used in preparation of
complexes are numerous and new methods keep emerging due to
advancement in technology. Some of these methods will be described in
this course. Two common reactions encountered for transition metal
coordination complexes are aquation and ligand substitution reactions.
Dissolution of a transition metal salt in water can be thought of as an
aquation reaction. In this type of reaction, water ligands coordinate to the
metal when the solid salt is placed in aqueous solution.

i. Direct Reaction
This involves combination reaction of metal salt and ligands in
liquid or gaseous state. This reaction can also be carried out in
suitable solvent if both reactants are solids. Examples are:

The product of the second reaction involving chromium salt is a

solid mass which may be difficult to handle but with the use of
inert solvent like toluene, the product can be easily filtered and dry
in purer state. In the third reaction, liquid ammonia is used which
can be allowed to evaporate to give the product.

ii. Substitution Reaction

The replacement of one ligand by another is the most common type
of reaction of coordination complexes, and the number of reactions
of this type is great. Some are carried out in aqueous solutions,
some in non-aqueous media, and others can be carried out in the
gas phase. Numerous examples of these reactions are common and
often carried out in qualitative test of cations using aqueous alkali
solution or ammonia.

28
CHM 423 MODULE 1

Substitution in Square Planar Complexes of Platinum

One observation from a large collection of experimental results is
that ligands not undergoing substitution themselves can influence
substitution at sites directly opposite them (trans) and, to a lesser
extent, at adjacent sites (cis). Examples lie with Pt(II) square
planar complexes, where some ligands show strong trans effect,
causing ligands directly opposite them to be more readily
substituted than those in cis position. Ligands opposite a chloro
ligand in a square planar platinum complex are substituted more
readily than those opposite an ammine ligand. Experimental
studies have produced an order of trans effects for various ligands
that coordinate to Pt(II).

CO > CN−>PH3> NO2−> I−>Br->Cl−>NH3>HO−> H2O

The importance of the order is that it can be used to predict the

products of reactions involving Pt square planar complexes and
products of other related complexes. In a reaction where a ligand
with stronger trans effect than Cl- is present, the chloro trans to
this ligand will be substituted instead of chloro ligand that is in cis
position to this ligand. The reason is because ligands with stronger
trans effect form bonds that are stronger with shorter bond length
hence making the ligand opposite them to be weak with longer
bond length. This makes such trans ligand more susceptible to
substitution. The following examples illustrate the influence of the
trans effect. Note that NH3 has less trans effect, therefore the
products of the first two reactions are cis, as expected; but CO
exhibits a stronger trans effect (the product of the last reaction
established this).

29
CHM 423 COORDINATION CHEMISTRY

iii. Reaction of Metal Salts

Two different metals salts, with suitable anion that can act as
ligand, combine together to form complex in such a way that the
anion will behave as ligand. Another related reaction is one
involving a complex and metal salt to produce a new complex.

iv. Partial Decomposition Reactions

These are reactions in which stable complexes are heated to derive
out volatile ligands in order to form new complexes. The
coordination number may change and in some cases it may remain
constant. The reactions occur in solid state.

v. Reduction and Oxidation Reaction

Many coordination complexes can be prepared when a compound
of the metal is either reduced or oxidised in the presence of a
ligand. The redox reaction can also occur between two complexes
where transfer of electron(s) can lead to new complexes. This
method is used to prepare complexes of metal ion in unstable
oxidation state. For example, Co(III) solution cannot be used to
prepare its complexes because it is very unstable due to its strong
oxidising ability. Complexes of the ion are prepared by oxidation

30
CHM 423 MODULE 1

of solution of Co(II) in the presence of ligand. The complexation

of the Co(III) helps to prevent reduction of this very strong metal
ion. Complexes of Cr(III) are also prepared in similar manner.

[Fe(CN)6]4- + [IrCl6]2- →[Fe(CN)6]3- + [IrCl6]3-

4CoCl2 + 8en + 4en.HCl + O2 → 4[Co(en)3]Cl3 + 2H2O
4CoCl2 + 8en + 8HCl + O2 → 4 trans-[Co(en)3Cl2]Cl.HCl +
2H2O
[Co(NH3)5Cl]2+ + [Cr(H2O)6]2+ + 5H2O → [Cr(H2O)5Cl]2+ +
[Co(H2O)6]2+ + 5NH3
[Co(NH3)5CN]2+ + [Cr(H2O)6]2+ + 5H2O → [Cr(H2O)5NC]2+ +
[Co(H2O)6]2+ + 5NH3
[Cr(H2O)5NC]2+ → [Cr(H2O)5CN]2+ (fast reaction).

SELF-ASSESSMENT EXERCISE

i. With the aid of equations only, show how reactions of metal salt
can be used to prepare two metal complexes.
ii. Discuss partial decomposition reaction in metal complex
preparation.

4.0 CONCLUSION
Preparation of complexes involves many reactions that include; simple
mixing of metal salts with ligands, substitution of one ligand with another
inside a complex, oxidation and reduction of complexes to effect change
in oxidation state and partial decomposition of complexes. Some of these
reactions are rapid and may occur within few seconds.

5.0 SUMMARY
Metal complexes can be prepared by different reaction procedures
depending on the desired end product. Reactions such as; direct
combination, substitution, decomposition, reduction and oxidation have
been used to prepare many complexes.

6.0 TUTOR-MARKED ASSIGNMENT

1. Discuss the following reactions in the preparation of metal
complexes
i. Direct reaction
ii. Substitution reaction
iii. Redox reaction (Time allowed: 9 mins).

2. Predict the products of the following reactions:

i. [PtCl3NH3]- + NH3 →
ii. [PtCl3NO2]2- + NH3 →

31
CHM 423 COORDINATION CHEMISTRY

iii. [PtCl(NH3)3]- + CN- →

iv. [PtCl3NH3]- + CO →
v. [PtCl3NH3]- + PH3 → (Time allowed: 10 mins).

7.0 REFERENCES/FURTHER READING

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rd ed.). Interscience Publishers, a Division of John Wiley and
Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry (2nd ed.).

Pearson Education Limited.

Miessler, G. L. & Tarr, D. A. (2010). Inorganic Chemistry (3rd ed.).

Pearson Education Int.

Primer (2019). Coordination Chemistry. Available online at:

https://sitesmedia.s3.amazonaws.com/chem/files/2013/01/Coordi
nation_chemistry_Primer.pdf.

32
CHM 423 MODULE 2

MODULE 2

UNIT 1 THEORIES OF STRUCTURE AND BONDING

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Valence Bond Theory
3.2 Crystal Field Theory
3.3 Ligand Field Theory and Molecular Orbital Theory
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

The attractive force which holds various constituents (atoms, ions, etc.)
together in different chemical species is called a chemical bond. Since the
formation of chemical compounds takes place as a result of combination
of atoms of various elements in different ways, it raises many questions.
Why do atoms combine? Why are only certain combinations possible?
Why do some atoms combine while certain others do not? Why do
molecules possess definite shapes? To answer such questions bonding in
coordination chemistry has been described by many theories. In order to
explain various properties exhibited by complexes, these theories were
modified. The theory of Effective Atomic Number (EAN) rule was first
used but found to be inadequate as behaviour of many complexes could
not be explained by these methods. The EAN rule states that stable
compound should have electronic configuration of its nearest noble gas.
There are many exceptions to this rule because it limits the coordination
number possible for each metal. Octahedral complexes of many
compounds show exception to this theory. However, the theory is
sufficient enough to explain the bonding in metal complexes with metal
in zero oxidation state. Examples are [Ni(CO)4] and [Cr(CO)6] where the
central metal has zero oxidation number and accommodates ligands
sufficient enough to have the electronic configuration of their nearest
noble gas. The theory cannot explain the reason for variation in
coordination number, hence the need for another theory. Valence bond
theory (VBT) is introduced to explain the reason for the variation in
coordination number based on the number of hybridised orbitals of the
metal used in bonding. It cannot explain fully the concept of colour and
magnetic properties of complexes. Crystal Field Theory (CFT) is used to
provide explanation for the spectra and magnetic properties of complexes.

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CHM 423 COORDINATION CHEMISTRY

Although, CFT is very useful, it cannot explain some degree of covalence

in some complexes. To be able to explain reason for some degree of
covalence in some complexes, the CFT is modified to Adjusted Crystal
Field Theory (ACFT) also called Ligand Field theory (LFT). Finally,
Molecular Orbital Theory (MOT) is introduced to fully explain the
various properties of complexes. To have indebt understanding of
bonding in complexes, these theories must be fully studied.

2.0 OBJECTIVES

By the end of this unit, you should be able to:

 state the theories used to describe bonding in metal complexes

 explain Valence Bond Theory (VBT)
 explain Crystal Field theory (CFT)
 explain Ligand Field Theory (LFT)
 explain Molecular Orbital Theory (MOT).

3.0 MAIN CONTENT

3.1 Valence Bond Theory

Valence bond theory (VBT) is a chemical bonding theory that explains

that bonding between two atoms is caused by the overlap of half-filled
atomic orbitals. The two atoms share each other's unpaired electron to
form a filled orbital to form a hybrid orbital and bond together. The VB
theory describes the formation of covalent bonds from the overlap of
atomic orbitals on two different atoms. Because of the overlap, it is highly
probable that pair of electrons are found in the physical region or space
where the orbitals overlap. Valence Bond Theory (VBT) describes
bonding in coordination complexes by considering the hybridisation of
the orbitals involved in the bonding and stereochemical consequences of
the hybridisation. This theory was first extended to explain bonding in
coordination complexes by Pauling in 1930. With the theory, He was able
to account for the stereochemistry and magnetic behaviour of many
complexes through the inner and outer orbital bonding concept. The
electronic configurations of the transition metals allow them to make use
of either 3d or 4d orbitals in coordination with ligands. Pauling described
complexes formed by the use of 3d orbitals as inner complexes and those
formed by the use of 4d orbitals as outer complexes. The inner orbital
complexes have lesser number of unpaired electrons compare to the
outerorbital complexes; hence, the inner orbital complexes are called low
spin complexes and the outer orbital complexes are called high spin
complexes. With this concept, Pauling was able to account for the
magnetic behaviour of some complexes. The nature of coordinating

34
CHM 423 MODULE 2

ligands determines the spin adopted by complexes. According to VBT,

coordination complexes are formed by:

i. Dissociation of the salt to make the cation (M+) available for

coordination.
ii. Hybridisation of atomic orbitals of the cation required to
accommodate the electron pairs to be donated.
iii. Rearrangement of electrons in the cation atomic orbitals, where
necessary to ensure that the hybridised orbitals are free to
accommodate the donated electron pairs.
iv. Bond formation between the cation and the ligands by overlapping
of atomic orbitals of ligands containing the lone pair and the
hybridised orbitals of the cation.
v. Spatial orientation of the ligands to minimise repulsion between
them leading to stereochemistry (shape) of the complex.

Stereochemistry in complexes depends on the type and number

(coordination number) of atomic orbitals of the central metal atom or ion
hybridised. Below is a Table showing possible structures for different
coordination number and hybridisation.

CN Atomic Orbital Hybrid type Structure Example

2 s, px sp Linear [Ag(CN)2]
3 s, px, py sp2 Trigonal planar [HgI3]-
4 s, px, py, pz Sp3 Tetrahedral [ZnCl4]2-
4 s, px, py,dx2-y2 dsp2 Square planar [Ni(CN)4]2-
5 s, px, py,pz, dz2 sp3d Trigonal [Cu(Cl)5]3-
bipyramidal
5 s, px, py,pz, dx2- sp3d Square [Cu(CN)5]3-
y2, pyramidal
6 s, px, py,pz, dx2- sp3d2 Octahedral [Cu(H2O)]2+
2 2
y ,dz
6 dx2-y2,dz2,s, px, d2sp3 Octahedral [Ni(CN)]4-
py,pz

The coloured arrows indicate the spins of the electrons of the donated
pairs while the dark arrows represent the spins of the metal. Generally,
tetrahedral complexes are high spin complexes while square planar
complexes are low spin complexes. The number of unpaired electrons
determines the magnitude of the magnetic properties of the complexes.
Complexes without unpaired electron are diamagnetic while those with
unpaired electrons are paramagnetic in nature. In [Ni(CN)4]2-, the two
unpaired electron in the Ni2+d orbitals are forced to pair up due to
approach of strong CN- ligand unlike Cl- which has less repulsion effect
on the unpaired electrons in [Ni(Cl)4]2- complex.

35
CHM 423 COORDINATION CHEMISTRY

Note that two electrons in Mn2+ are forced to pair up in [Mn(NO2)6]3- due
to approach of the strong ligand (NO2-) while in the hexaaqua complex of
Mn3+, these electrons remained unpaired.

Valence bond theory limitations:

 It cannot explain relative stability of complexes
 It cannot explain colours and spectra of complexes.

3.2 Crystal Field Theory (CFT)

Crystal Field Theory (CFT) describes the breaking of degeneracies of

electron orbital states, usually d or f orbitals, due to a static electric field
produced by a surrounding charge distribution (anion neighbours). At
almost exactly the same time that chemists were developing the valence-
bond model for coordination complexes, physicists such as Hans Bethe,
John Van Vleck, and Leslie Orgel were developing an alternative known
as crystal field theory. This theory tried to describe the effect of the
electrical field of neighbouring ions on the energies of the valence orbitals
of an ion in a crystal. There are several characteristics of coordination
complexes that are not satisfactorily explained by VBT description of the
bonding. For example, the magnetic moment of [CoF6]3- shows that there

36
CHM 423 MODULE 2

are four unpaired electrons in the complex, whereas that of [Co(NH3)6]3-

shows that this complex has zero unpaired electrons, although in the two
complexes Co3+ is a d6 ion. In VBT, the bonding types in these complexes
are shown to involve sp3d2 and d2sp3 hybrid orbitals respectively, but that
does not provide an explanation as to why the two cases exist. Another
aspect that is inadequately explained by VBT approach is the number and
type of absorption bands observed in the spectra of complexes. One of the
most successful approaches to explaining these characteristics is known
as crystal field theory. Crystal field theory was developed by considering
two compounds: manganese(II) oxide, MnO, and copper(I) chloride,
CuCl.

When a metal ion is surrounded by anions in a crystal, there is an

electrostatic force (field) produced by the anions that changes the energies
of the d orbitals of the metal centre. The field produced is known as a
crystal field. Crystal field theory was introduced in 1929 by Hans Bethe
to explain the spectral characteristics of metal complexes. This is a purely
electrostatic model which assumes electrostatic interaction between
positively charged metal centre and negatively charged anions or polar
molecules. Unlike VBT, CFT predicts properties of complexes based on
repulsion between electrons of the metal and those of the ligands in a
complex. The positive charge on the metal is assumed to be the source of
attraction for the ligands however; the ligands are also repelled by the d-
orbital electrons of the metal. The repulsion on the d-orbital electrons is
not uniform leading to splitting of the d-orbitals. The splitting of the
orbitals results in loss of degeneracy among the 5 d-orbitals. The pattern
of splitting is dependent on the coordination number and stereochemistry
of the complex. CFT approach considers the metal as positive point
charge and the ligands as negative point charges. The ligands move
towards the centre of the metal in the direction of the coordinates related
to the shape to be adopted by the metal.

Octahedral Field
Before the resultant effect of the field around a metal centre generated by
the ligands can be illustrated, it is important to have an understanding of
the shapes and orientations of the d orbitals of the metal. The set of five
d-orbitals are shown below. In free gaseous metal ion, the five orbitals are
degenerate (of equal energy). The five orbitals remain degenerate in a
spherical electrostatic field with a higher energy since all will be equally
raised by the same amount. An octahedral complex can be considered as
a metal ion approached by six ligands along the x, y and z axes. When six
ligands surround the metal ion, the degeneracy of the d orbitals is lost
because three of the orbitals; dxy, dyz and dxz orbitals, are directed between
the axes while the others, dx2-y2 and dz2, are directed along the axes
pointing at the ligands. Therefore, there is greater repulsion between the
electrons in orbitals on the ligands and the dx2-y2 and the dz2 orbitals than

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CHM 423 COORDINATION CHEMISTRY

there is toward the dxy, dyz and dxz orbitals. Because of the electrostatic
field produced by the ligands, all of the d orbitals are raised in energy, but
two of them are raised more than the other three.

The two orbitals of higher energy are designated as the eg orbitals, and the
three orbitals of lower energy make up the t2g orbitals. The “g” subscript
implies being symmetrical with respect to a centre that is present in a
structure that has octahedral symmetry. The “t” refers to a triply
degenerate set of orbitals, whereas “e” refers to a set that is doubly
degenerate. The energy separating the two groups of orbitals is called the
crystal splitting, Δ0. Splitting of the energies of the d orbitals occurs in
such a way that the overall energy remains unchanged and the “center of
energy” (barycentre) is maintained. The eg orbitals are raised 1.5 times as
much as the t2g orbitals are lowered from the center of energy. Although,
the splitting of the d orbitals in an octahedral field is represented as Δo, it
is also sometimes represented as 10 Dq, where Dq is an energy unit for a
particular complex. The two orbitals of the eg, are raised by 3/5Δo or 6Dq
while the t2g orbitals are lowered by 2/5Δo or 4dq relative to barycentre.
The crystal splitting (Δo) determines the energy required for an electron
to be promoted from the lower energy level or orbital to the higher energy
level. Δo depends on the nature of the ligand the stronger or higher the
electrostatic force generated by the approach of the ligand the greater Δo.
For electron to be promoted to a higher energy level, it must absorb light
energy with wavelength equivalent to Δo.

38
CHM 423 MODULE 2

The effect of crystal field splitting is easily observed by studying the

absorption spectrum of [Ti(H2O)6]3+ since Ti3+ ion has 3d1 outer
electronic configuration. In the octahedral field generated by the six H2O,
the 3d orbitals split in energy. The only transition possible is promotion
of the electron from an orbital in the t2g set to one in the eg set. This
transition shows a single absorption band, the maximum of which
corresponds directly to the energy represented as Δo. As expected, the
spectrum shows a single, broad band that is centred at 20,300 cm-1. This
energy (243 kJmol-1) is large enough to cause other effects when a metal
ion is surrounded by six ligands. However, only for a single electron
system is the interpretation of the spectrum simple. With multiple
electrons in the d-orbitals, the electrons interact by spin-orbit coupling
leading to complication in the interpretation of the spectra.

Spectrochemical Series
Ligand Series
If several complexes of the same metal ion and the same coordination
number are prepared using different ligands, the positions of the
absorption bands will be shifted to higher or lower wave numbers
depending on the nature of the ligand. In this manner, it is possible to
arrange ligands according to their ligand field splitting capacity. The
series of ligands arranged this way is called the spectrochemical series of
the ligands.

CO ~ CN-> NO2->en> NH3>py> NCS-> H2O ~ ox > OH-> F-> Cl-> SCN-
> Br-> I-
Strong field Weak field

Differences between the splitting produced by adjacent members in the

series are small, and the order is approximate in some cases ([Fe(H2O)6]3+
= 14, 000 cm-1 and in [Fe(ox)3]3- = 14, 140 cm-1), especially when
different metal ions or metal ions in different rows of the periodic table
are considered. For example, the order of the halide ions is changed if the
metal ion is from the second transition series. The spectrochemical series
is a very useful guide because reversals between rather widely separated
members such as NO2- and NH3 do not take place. Ligands that force
electron pairing are known as strong field ligands, and these ligands can
be expected to give low-spin octahedral complexes with first-row metal
ions. Weak field ligands are known to give high-spin octahedral
complexes with first-row metal ions.

Metal Ion Series

It is possible to range metal ions in terms of the splitting of the d orbitals
produced by a given ligand and stereochemistry. The arrangement which
is independent of the nature of the ligand is called spectrochemical series
of the metal ions. From the series, it can be observed that the higher the

39
CHM 423 COORDINATION CHEMISTRY

oxidation state the greater the splitting. For first-row metal ions the
arrangement is

Mn3+> Co3+> V3+> Cr3+> Fe3+> V2+> Fe2+> Co2+> Ni2+> Mn2+

Δo for Octahedral Complexes of First-Row Transition

Metal Ions (cm-1)
METAL LIGANDS
ION
F- H2 O NH3 CN-
Co3+ - 20, 800 22, 900 33, 000
V3+ 16, 100 18, 500 - 26, 600
Cr3+ 15, 100 17, 900 21, 600 26, 600
Fe3+ 14, 000 14, 000 - -

Jahn Teller Distortions

The Jahn-Teller effect is a geometric distortion of a non-linear molecular
system that reduces its symmetry and energy. This distortion is typically
observed among octahedral complexes where the two axial bonds can be
shorter or longer than those of the equatorial bonds. Jahn Teller theory
states that any nonlinear molecular system in a degenerate electronic state
will be unstable and will undergo some sort of geometrical distortion to
lower its symmetry and remove the degeneracy. Distortion is inevitable if
there is unsymmetrical occupation of degenerate orbitals. This theorem
was postulated by Hermann Jahn and Edward Teller in 1937. Metal ions
with d9 (Cu2+) and d4 (Cr2+) high spin in octahedral field are known to
have distorted octahedral shapes due to unequal number of electrons
occupying the eg orbitals. With nine electrons, the two orbitals of eg
cannot contain the same number of electrons, there will be two electrons
in one orbital and one electron in the other. The orbital with two electrons
will have greater repulsion for ligands on its axis compare to the orbital
with one electron. Therefore, all the ligand-metal bond length will not be
equal hence distortion occurs in the complex. If the orbital with the greater
number of electron is dz2, the ligands along the z-axis will not be as close
to the metal centre as others. The ligands in dz2 direction will have longer
ligand-metal bond length. This will result in elongation distortion. If the
dx2-y2 contains greater number of electron compare to dz2 in an octahedral
field, the ligands along the x and y plane will experience greater repulsion
leading to increase in length of the ligands along the equatorial region.

The d9 configuration is not the only one for which distortion leads to a
lower energy. The d4 high-spin configuration will have one electron in
every of the four lowest-lying orbitals with an energy that is lower as a
result of splitting the dx2-y2 and dz2 orbitals. The Cr2+ ion has d4
configuration, distortion is expected to occur for complexes of this ion,
and this is indeed the case. Similarly, a distortion would be predicted for

40
CHM 423 MODULE 2

a d1 or d2 ion, for which the electrons would be located in the two orbitals
of lowest energy. However, the magnitude of splitting in t2g is much
smaller than that of egbecause the orbitals involved are directed between
the axes, not at the ligands. These are non-bonding orbitals, so the effect
of moving the ligands on the z axis farther from the metal ion is much
smaller. The result is that any distortion involving metals with these
configurations is very small. This type of distortion is called compression.
Distortion is also possible in tetrahedral complexes but not as pronounced
as in octahedral complexes.
ELONGATION COMPRESSION

dz2 dx2-y2 dz2 dx2-y2 dz2 dx2-y2 dz2 dx2-y2

dxy dxz dyz dxy dxz dyz dxy dxz dyz dxy dxz dyz
d4 d9 d4
d9
axial
dx2-y2 axial
dz2 equitorial
M
dz2 dx2-y2
M equitorial
dxy dxz dyz

dxy
dxz dyz

Tetrahedral Field
It is important to note that not all complexes are octahedral or even have
six ligands bonded to the metal ion. Therefore, there is need to study
behaviour of other possible crystal fields. Many complexes are known to
have tetrahedral symmetry hence, the need to determine the effect of a
tetrahedral field on the d orbitals. In a tetrahedral field, none of the metal’s
d orbitals point exactly in the direction of the ligands rather they are in
between the ligands in the crystal field. However, the triply generate
orbitals (dxy, dyz and dxz) are closer to the ligands’ path on approaching the
metal centre than the doubly generate orbitals (dx2-y2 and dz2). The result
is that the dxy, dyz and dxz orbitals are higher in energy than are the dx2-y2
and dz2 orbitals because of the difference in how close they are to the
ligands. In a simple language, the splitting pattern produced by a
tetrahedral field is an inversion of an octahedral field’s splitting pattern.
The magnitude of the splitting in a tetrahedral field is designated as Δt.
There are differences between the splitting in octahedral and tetrahedral
fields. The two sets of orbitals are inverted in energy and the splitting in
the tetrahedral field is much smaller than that produced by an octahedral
field. Reasons; there are only four ligands producing the field rather than
the six ligands in the octahedral complex, none of the d orbitals point
directly at the ligands in the tetrahedral field and in an octahedral

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CHM 423 COORDINATION CHEMISTRY

complex, two of the orbitals point directly toward the ligands and three
point between them. This results in a maximum energy splitting of the d
orbitals in an octahedral field. In fact, it can be shown that if identical
ligands are present in the complexes and the metal-to-ligand distances are
related, Δt = (4/9) Δo. This difference in energy value explains the reason
why tetrahedral complexes are rare or simply put do not exist because the
splitting of the d orbitals is not large enough to force electron pairing.
Also, because there are only four ligands surrounding the metal ion in a
tetrahedral field, the energy of all of the d orbitals is raised less than they
are in an octahedral complex. No symmetry symbol is required to describe
the bond in tetrahedral field because there is no centre of symmetry in a
tetrahedral structure.

Square Planar Complex

A square planar arrangement of ligands can be obtained from octahedral
model by removal of the two ligands point directly along the z axis. This
will result in decrease in repulsion experienced along the z-axis and
orbitals with z component will experience decrease in energy and greater
stability. The energy of dz2, dxz and dyz will be reduced while those of dx2-
2
y and dxy will increase. The orbital arrangement in square planar complex
is shown below. Metal ions with d8 (Ni2+, Pt2+ and Pd2+) configuration are
known to form square planar complexes which are diamagnetic in nature
resulting from relatively large difference in energy of dxy and dx2-y2
forcing the electrons to pair in orbital of lower energy level.

42
CHM 423 MODULE 2

Factors Affecting Crystal Field Splitting

i. The nature of the ligands- the smaller the size of the anions the
greater the splitting. This can be observed with the halides F->Cl-
> Br-> I-. Similarly, ligands with ability to form π-bond cause
greater splitting. Co > CN->phen>NO2-.
ii. The higher the oxidation state or the primary valence of the metal,
the greater the splitting. Generally, M3+ ions cause greater splitting
than M2+ ions.
iii. The type of d-orbital involved in the bonding scheme, the splitting
pattern in 5d is the greatest because it spread more into space than
others. The observed trend is 3d < 4d < 5d e.g. [Co(H2O)6]3+ = 20,
800 cm-1 and [Rh(H2O)6]3+ = 27, 200 cm-1

Limitation of Crystal Field Theory (CFT)

Although, crystal field theory provides insight to spectra and magnetic
properties of complexes through the concept of strong and weak field
ligands, it cannot account for the position of these ligands on the
spectrochemical series and it cannot also explain the reason why some
degree of covalency is observed in a number of complexes.

3.3 Ligand Field Theory and Molecular Orbital Theory

The crystal field theory is modified to take into account the existence of
some degree of covalency in transition complexes based on the evidence
from electron spin resonance spectra which shows that certain percentage
of the electrons is diffused into the ligand orbital. Consequently, the bond
existing in complexes is not purely electrostatic. The modification of CFT
results into Adjusted Crystal Field Theory also called Ligand Field
Theory (LFT). If the degree of diffusion or overlap is in excess, the LFT
will not hold rather a pure covalent treatment will be suitable hence the

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CHM 423 COORDINATION CHEMISTRY

use of Molecular Orbital Theory (MOT). The LFT can be considered as a

mid-point between electrostatic and covalent description of bonding in
metal complexes. The LFT is purely a parameter based model involving
the uses of experimentally derived data or parameters like Crystal Field
Stabilisation Energy, and Racah parameters, which are derived from
electronic spectra of complexes.

Molecular Orbital Theory is the result of overlap of bonding atomic

orbital of the ligands and the hybridized orbital of the metal leading to
formation of both bonding and antibonding molecular orbitals. In a
molecular bonding scheme, the numbers of bonding and antibonding
orbitals are equal but the antibonding orbitals canceled out the resultant
effect of the bonding orbitals.

Molecular Orbital Theory in an octahedral complex can be illustrated with

complex [Co(NH3)6]3+ in which metal–ligand σ-bonding is dominant. In
the construction of a molecular orbital energy level diagram for such a
complex, many approximations are made and the outcome is considered
to be qualitatively accurate. Despite this, the results provide useful
explanation on metal–ligand bonding.

Cr3+ is a first-row metal, the valence shell atomic orbitals are 3d, 4s and
4p. In octahedral symmetry, the s orbital has a1g symmetry, the p orbitals
are degenerate with t1u symmetry, and the d orbitals split into two sets
with eg (dz2 and dx2-y2) and t2g (dxy, dyz and dxz) symmetries. Each ligand,
NH3, provides one orbital. Six orbitals from the ligands are assigned a1g,
t1u and eg symmetries. The nine valence orbitals of the metal are grouped
into bonding and non-bonding orbitals, the bonding orbitals are; 4s, 3px,
3py, 3pz, dx2-y2 and dz2 which are in the direction of the approaching hence
suitable for overlapping. The t2g set (dxy, dxz, dyz) which are not exactly in
the direction of the approaching ligands are considered non-bonding. The
diagram below shows the molecular orbital arrangement for the complex
[Co(NH3)6]3+. The six ligand orbitals and six orbitals of the metal are
grouped into six bonding molecular orbitals and six antibonding
molecular orbitals, while t2g orbitals are left as non-bonding molecular
orbitals. Electrons from the ligands are filled into the bonding orbitals
while the d electron are filled into non-bonding t2g orbitals and Lowest
unoccupied Molecular Orbital (LUMO) which are the antibonding
orbitals representing the eg set of the metal d orbitals.

44
CHM 423 MODULE 2

The Nephelauxetic Effect

A metal ion surrounded by ligands in a complex will experience changes
in the total electron environment of the metal ion when compare to the
environment in the un-complexed metal ion due to the coordinated
ligands. One consequence is that the energy required to pair up electron
will be altered. Although, the energy necessary to pair up electron in free
metal ion can be easily estimated from the appropriate spectroscopic data,
this is not applicable to a metal ion that is contained in a complex. When
ligands bind to a metal ion, the orbitals on the metal ion are spread out
over a larger region of space and extend to the orbitals of the ligand. In
molecular orbital terminology, the d-orbital electrons of the metal ion
become more delocalised in the complex than they are in the free ion. This
expansion of the electron cloud is called the nephelauxetic effect. As a
result of the nephelauxetic effect, the energy required to pair up electrons
in the metal ion is somewhat smaller than it is for the free ion. When
ligands such as CN-, CO and NO2- are present, the nephelauxetic effect is
quite large owing to the ability of the ligands to π bond to the metal as a
result of back donation.

For complexes with a common metal ion, it is found that the

nephelauxetic effect of ligands varies according to a series independent
of metal ion:

F-< H2O < NH3< en < ox2-< NCS-< Cl-< CN-< Br-< I-
A nephelauxetic series for metal ions independent of ligands is:
Mn2+< Ni2+< Co2+< Mo2+< Re4+< Fe3+< Ir3+< Co3+< Mn4+

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CHM 423 COORDINATION CHEMISTRY

SELF ASSESSMENT EXERCISE

i. Which of the following options is not a factor affecting crystal field

splitting?
ii. The triply generate orbitals in tetrahedral field are the following
except
iii. Metal ions with ____configuration are known to form square
planar complexes
iv. What is Jahn-Teller effect? Hence, where does it occur?

4.0 CONCLUSION

The bonding theories in coordination chemistry provide insight to

properties of transition metal complexes. Valence Bond Theory explains
the shape and predicts magnetic properties of complexes based on
hybridised orbitals of the metals but fails to explain the colour and spectra
properties of metal complexes. Crystal Field Theory is a very important
model that explains the spectra properties of complexes based on
electrostatic treatment of the bonding mode in complexes. Ligand Field
and Molecular Orbital theory provide information on how some degree of
covalence exists within complexes contrary to the pure electrostatic
treatment of CFT.

5.0 SUMMARY

From bonding theories in coordination chemistry, the following

deductions can be made:

 The shape of complex is determined by coordination number,

hybridisation and type of atomic orbitals of the metal hybridised.
 With concept of inner and outer orbital complexes, magnetic
properties of low and high spin complexes can be predicted.
 Electrostatic treatment of bonding in complexes provides
information on colour and spectra of complexes.
 The Ligand Field and Molecular Orbital theories help to explain
the concept of covalence observed in some complexes.
 With the same metal and stereochemistry, ligands can be arranged
based on their ability to cause crystal field splitting, which gives
rise to spectrochemical series of the ligand. Similarly, a
spectrochemical series is observed with metal ions when the same
ligand and stereochemistry are employed.
 On complexation the pairing energy of the metal ion is less than
that in free metal ion. This is due to the influence of the ligand
resulting into the nephelauxetic effect.

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CHM 423 MODULE 2

6.0 TUTOR-MARKED ASSIGNMENT

1. The complexes [NiCl2(PPh3)2] and [PdCl2(PPh3)2] are

paramagnetic and diamagnetic respectively. What is the
implication of these magnetic properties about their structures?
(Time allowed: 10 mins)

2. The anion [Ni(SPh4)]2- is tetrahedral. Explain why it is

paramagnetic. (Time allowed: 5 mins)

3. For each of the following complexes, give the hybrid orbital type
and the number of unpaired electrons: [Co (H2O)6]2+, [FeCl6]3-,
[PdCl4]2-, [Cr(H2O)6]2+and [Mn(NO2)6]3- (Time allowed: 15 mins)

4. Which of the following complexes would undergo Jahn-Teller

distortion? (Time allowed: 7 mins)

5. Draw the molecular orbital diagram of [CoF6]3- and [MnCl6]3-

(Time allowed: 8 mins)

7.0 REFERENCES/FURTHER READING

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rd ed.). Interscience Publishers, a Division of John Wiley and
Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

Figgis, B. N. & Hitchman, M. A. (2000). Ligand Field Theory and Its

Applications. New York: Wiley.

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry (2nd ed.).

Pearson Education Limited.

Miessler, G. L. & Tarr, D. A. (2010). Inorganic Chemistry (3rd ed.).

Pearson Education Int.

Kettle, S. F. A. (1998). Physical Inorganic Chemistry: A Coordination

Approach. New York: Oxford University Press.

Porterfield, W. W. (1993). Inorganic Chemistry: A Unified Approach,

(2nd ed.). San Diego, CA.: Academic Press.

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CHM 423 COORDINATION CHEMISTRY

Video Link “Chemical Bonding and Molecular Structure (2019). Study

Guide Available online and retrieved on June 5, 2019 at:
https://study.com/academy/topic/chemical-bonding-molecular-
structure.html

Video Link “Jahn Teller Effect”StudyGuide Available at:

https://www.youtube.com/watch?v=XwQITEKVb4o

48
CHM 423 MODULE 3

MODULE 3

UNIT 1 PHYSICAL METHODS OF STRUCTURAL

INVESTIGATION

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Methods used in Structural Investigation of Complexes
3.2 Electronic Spectroscopy
3.3 Vibrational Spectroscopy
3.4 Magnetic Measurement
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

In simple language, physical methods of structural investigation are

processes of acquiring and collecting required and valuable information
about a newly synthesised complex. Much of what we know today about
properties of complexes comes from physical methods of structural
investigation. Working at the atomic and molecular level, physical
methods of structural investigation involves the application of an array of
physical methods which can provide information on the complex under
investigation. Since there are many methods, it is important to know the
method most suitable for acquiring the information desired. Once a new
complex is synthesised and purified, the first investigation is to know the
elements that constitute the complex which relates to the chemical
composition. The next investigation should be on the shape of the
complex, which is a far more complex involving defining what
components are involved and how they are assembled together.

Synthesis and purification of complexes may be difficult; the processes

involved in structural investigation are more complex and multi-tasking.
Defining molecular structure in both solution and the solid state requires
a wide range of physical methods for characterisation. Quite a number of
physical methods have been employed to study properties of metal
complexes in order to provide information on molecular structure and
reactivity. Characterisation in metal complexes includes isolating a
complex in the solid state. This process is difficult and may be
complicated if there exist differences in the nature of the complex in
solution and the solid state. Physical methods employed in

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CHM 423 COORDINATION CHEMISTRY

characterisation of complexes include; electronic absorption

spectroscopy, vibrational spectroscopy, magnetic measurement,
conductivity, elemental analysis, thermal analysis, x-ray crystallography,
mass spectroscopy, nuclear magnetic resonance, electron spin resonance
and others. The list is actually endless as different methods are used for
different purposes of investigating properties of complexes. It is therefore
important to acquire knowledge on some of these investigative methods.

2.0 OBJECTIVES
By the end of this unit, you should be able to:

 state various methods used in structural investigation of complexes

 explain the principle and use of electronic spectroscopy in
structural investigation of complexes
 explain the principle and use of vibrational spectroscopy in
structural investigation of complexes
 explain the principle and use of magnetic measurement in
structural investigation of complexes.

3.0 MAIN CONTENT

3.1 Method used in Structural Investigation of Complexes

Comprehensive structural investigation of complexes involves many
analyses providing different kinds of information on nature and structure
of complexes. It is therefore important to know what information can be
acquired from each analysis carried out on complexes.

Elemental analysis of a pure complex will provide information on the

percentage composition of the various elements (C, H, N and S) that
constitute the complex. This will help to predict a suitable formula for the
complex. Thermal analysis may be carried out to determine change in
mass with temperature. This helps to know the number of waters of
crystallisation present in complex and also helps to determine the heat
stability of the complex.

Conductivity measurement helps to distinguish between ionic and neutral

complexes. Magnetic properties of complexes are obtained through
magnetic measurement. Electronic (UV-VIS) spectroscopy provides
information on the geometry of complexes and vibrational spectroscopy
helps to determine the possible binding site(s) of ligand to complex. The
molecular mass of a complex can be obtained with mass spectroscopy. If
a suitable crystal of a complex is available, x-ray crystallography can be
used to establish the structure of the complex. Other forms of analyses are
also carried out to obtain more information on other properties of
complexes.

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CHM 423 MODULE 3

It is not enough to know the various techniques used in structural

investigation of complexes, it is very important to get acquainted to the
principles behind some of these analyses to facilitate interpretation and
understanding of results obtained from them. This course shall focus on
electronic spectroscopy, vibrational spectroscopy and magnetic
measurement.

3.2 Electronic Spectroscopy

One of the notable characteristics of the transition metal ions and their
complexes is their colourful appearances. This is attributed to the partial
filling of the d-orbitals, which makes them capable of absorbing light
energy in the visible region leading to electronic transitions between
different energy levels within split d-orbitals. In an electronic transition,
an electron is excited from an occupied to an empty orbital. The energy
of such transitions normally corresponds to light in the near IR, visible or
UV region of the electromagnetic spectrum. In d-block complexes,
various types of electronic transitions are possible depending on the
nature of their constituents. Some of these transitions occur within the
ligand (intra-ligand transition), within the split d-orbitals (ligand field or
d-d transition) and/or between the metal d-orbitals and ligand orbitals
(charge transfer transition).

To provide explanation on the colours of complexes, it is necessary to

have understanding of complementary colours. When light of a particular
colour is absorbed by a complex, the complementary colour to the
absorbed colour is observed. For example, when white light (containing
a broad spectrum of all visible wavelengths) is allowed to pass through a
substance that has capacity to absorb blue light, the substance will appear
in orange since the complementary colour of blue is orange. A simple way
to remember complementary colour is shown below using colour wheel.

When light intensity Io is allowed to pass through a standard solution of a

complex in a UV/Visible spectrophotometer, electron(s) in the complex
will absorb part of the light and be promoted to a higher energy level while
the unabsorbed light with intensity I will be transmitted through the
solution. A graph of log [Io/I] (Absorbance) can be made against

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CHM 423 COORDINATION CHEMISTRY

wavelength in nm. This plot is known as the electronic absorption

spectrum from which the various absorptions of the compound can be
determined. The intensity of the absorption (molar absorptivity (ε)) can
also be determined using Beer-Lambert Law, mathematically expressed
as; ε = A/lc, A = absorbance, l = path length (cm) through the solution
and c = concentration in mol/ dm3. The unit of ε is . It is possible to
calculate wave number (ν) in cm-1 equivalent to the wave length (λ) using
the expression: ν = ⁄ . With high ε, complexes are intensely coloured
and appear very bright.

Electronic Transitions in Complexes

Transitions in complexes can be grouped into three categories; intra-
ligand transitions, ligand field transitions and charge transfer transitions.

INTRALIGAND TRANSITIONS
These are transitions that depend on the nature of the chromophores
(group of atoms capable of absorbing light energy) present in the ligands.
These chromophores include organic functional groups such as alkenes,
aromatic hydrocarbons, heterocyclic compounds, amines, alcohols and
ethers.

n→σ* transition: In saturated molecules containing heteroatoms with

non-bonding lone pairs of electrons, the transition of the lowest energy
will be n→σ*. This is possible because both the bonding and non-bonding
orbitals are filled with electron and the highest occupied molecular orbital
(HOMO) is the non-bonding orbital n while the lowest unoccupied
molecular orbital (LUMO) is antibonding σ*. Examples of ligands with
this transition are; amines, alcohols, ammonia, water and ethers.

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CHM 423 MODULE 3

n→π* transition: This is possible in ligands with both non-bonding and

π bonding molecular orbitals. In such a ligand, the HOMO will be n,
LUMO will be π* and transition with the lowest energy will be n→π*.
Examples of such ligands are aldehydes (R-CHO), ketones (R-CO-R),
esters (RCOOR), amides (RCONH2) and carboxylic acids (RCOOH).
π→π* transition: Ligands containing double bonds or triple bonds
without any heteroatom will have transition of lowest possible energy to
be π→π*. Examples are olefins, conjugated dienes and aromatic
hydrocarbons.
Unsaturated heterocyclic compounds (such as 1, 10-phenanthroline, 2,2’-
bipyridine and pyridine, multiple transitions) have different transitions
including; π→π*, n→π* and n→σ*. The ligand transitions are often in
the ultra violet range of the spectrum but with extended conjugations,
some transitions in the visible regions will be inevitable.
Charge Transfer Transitions
Optical spectroscopy provides detailed experimental information on
many categories of charge-transfer transitions, bands that can be observed
for a wide variety of compounds. Electron can be excited from a metal
orbital to ligand orbital in a transition complex. This is made possible
when, the metal has electron in t2g orbitals (which are non-bonding
orbitals) and the ligand has suitable empty orbitals (π*). The transition of
electron in this process will lead to decrease in electron density around
the metal centre (oxidation). This transition is called Metal to Ligand
Charge Transfer (MLCT) transition commonly found in complexes with
metal ion in low oxidation state, which can be easily oxidised. Examples
are complexes of Ti3+ and Cu+. Generally, Charge Transfer (CT)
transitions are more intense and may likely mask d-d transitions though
they occur at higher wave number usually above 40, 000cm-1 with molar
absorptivity above 10, 000 L mol-1 cm-1. This is because the CT transitions
are spin-allowed and Laporte-allowed. However, d-d transitions are only
spin-allowed.
What can be tagged the reverse of MLCT is Ligand to Metal Charge
Transfer (LMCT) where electron density is transferred to the metal, which
is therefore reduced in the excited state. The higher the oxidation state of
the metal concerned, the easier such reduction will be, and so the lower
the LMCT energy. LMCT transitions in the visible region of the spectrum
give intense colour, as is found with permanganate (MnO4-) a d0 complex,
in which no d-d transition is expected. Other examples are: TiF62-, CrO42-
and TcO4-.
In a complex with two metal ions in different oxidation state, there may
be transfer of electron from orbital of metal in lower oxidation state to
that in higher oxidation state. This transition is called Metal to Metal
Charge Transfer and it can be observed in KFe[Fe(SCN)6] and
[[AuIIICl4][AuICl2]]2-.

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CHM 423 COORDINATION CHEMISTRY

Ligand Field Spectra (d-d Transitions)

Ligand field spectra result from the transition within metal d-orbitals
which have been split due to the ligand field on coordination. They are
also called d-d transitions because they occur within d-orbitals. For proper
understanding of d-d transitions, knowledge of interactions between
electrons in the d-orbitals is highly essential. An electron in a given atom
has a set of four quantum numbers; the principal (n), the subsidiary (l),
the magnetic (m) and the spin quantum numbers. Interaction can occur
between spin angular momentum and orbital angular momentum of the
single electron. However, if two or more unpaired electrons are present
with an atom, three different interactions are possible between the angular
momenta; spin-spin, orbit-orbit and spin-orbit interactions. The angular
momenta are vector quantities that interact (couple) in accord with
quantum-mechanical rules. In spin-spin coupling schemes, the spin
angular momenta of the electrons couple to give an overall resultant
spin(S). Similarly, the orbital angular momenta of the electrons couple to
give an overall resultant orbital angular momentum (L). The resulting
vector quantities (S and L) couple to give the total angular momentum
vector (J) for the atom.

Coupling occurs by this scheme, which is known as L-S or Russell-

Saunders coupling. The coupling scheme can be expressed as;
S = ∑ si= s1 + s2, s1 + s2 – 1, ...., s1-s2, where S represents vector sum of the
resultant spin angular momenta and si represents the spin of the individual
electron.

L = ∑li = l1 +l2, l1 + l2 – 1, ...., l1-l2, where L represents vector sum of the

resultant orbital angular momenta and li represents the orbital angular
momentum of the individual electron.

J = L + S= L +S, L + S – 1, ...., L-S, where J represents vector sum of the

resultant orbital and spin angular momenta.
Under Russell-Saunders coupling, the spin-spin coupling is assumed to
be greater than orbit-orbit coupling which is also greater than spin-orbit
coupling for the first-row transition metals.

Examples: for d1 electronic configuration, s = +1/2 and l = 2, since only

one electron is involved only spin-orbit coupling is applicable. J = 2 + 1/2,
2 – 1/2. J = 5/2 and 3/2.

Note that spin of electron is either -1/2 or +1/2 and atomic orbitals
designated as s, p, d, and f have values 0, 1, 2, 3 and 4 respectively.

In a manner similar to that by which the atomic orbitals are designated as

s, p, d, or f, the letters S, P, D, and F correspond to the values of 0, 1, 2,
and 3, respectively, for the resultant angular momentum vector (L). After

54
CHM 423 MODULE 3

the values of the vectors L, S, and J have been determined, the overall
angular momentum is described by a symbol known as a term symbol or
spectroscopic state. This symbol is constructed as (2S + 1)LJ where the
quantity (2S + 1) is known as the multiplicity. For one unpaired electron
system s= +1/2, (2(1/2)+ 1) = 2, and a multiplicity of 2 implies doublet state.
Therefore, for one unpaired electron system, the following are obtained S
= 1/2, L = 2 and J= 5/2 and 3/2, which give the term symbols 2D5/2 and 2D3/2.

The spectroscopic terms for d1 and d9 are the same as both contain the
same number of unpaired electron. Other related d-configurations with
the same term symbols can be determined using expression dn = d10-n.

For d2 and d8 configurations, the term symbols can be similarly

determined. These are two electron systems with s1 =
1 1
+ /2, s2 = + /2, l1 = 2 and l2 = 2
S = s1 + s2, s1 + s2 – 1, ...., s1-s2 = 1 and 0 L = l1 +l2, l1 + l2 – 1, ...., l1-l2 =
4, 3, 2, 1 and 0

J = L + S= L +S, L + S – 1, L-S, with L = 4 and S = 1 J = 5, 4, 3 multiplicity

is 2(1) + 1= 3

Term symbols are 3G5, 3G4 and 3G3. Other symbols are derived in similar
manner;
With L = 3 and S = 1, J = 4, 3, 2 Term symbols are 3F4, 3F3 and 3F2
With L = 2 and S = 1, J = 3, 2, 1 Term symbols are 3D3, 3D2 and 3D1
With L = 1 and S = 1, J = 2, 1, 0 Term symbols are 3P2, 3P1 and 3P0
With L = 4 and S = 0, J = 4 Term symbols are 1G4 Note 2(0) + 1 =
1 singlet state
With L = 3 and S = 0, J = 3 Term symbols are 1F3
With L = 2 and S = 0, J = 2 Term symbols are 1D2
With L = 1 and S = 0, J = 1 Term symbols are 1P1
With L = 0 and S = 0, J = 0 Term symbols are 1S0

NOTE: L; 0, 1, 2, 3, 4, 5 and 6 have symbols S, P, D, F, G, H and I

Not all the derived terms are allowed by Pauling exclusion principle,
which states that no two electrons must have the same values for the four
quantum numbers in a given atom, and Hund’s rule which states that
degenerate states must be singly filled before pairing.

To determine the allowed term symbols, the microstates of the electronic

configuration must be generated and then arranged to obtain the derived
term symbols. This is a very complex but interesting process that must be
carefully studied in order to have indebt knowledge of electronic
transition. The microstate for d1 and d9 is shown below;

55
CHM 423 COORDINATION CHEMISTRY

S = 1/2, MS = , − 1, … . , , … . . , − , Ms = +1/2, -1/2. Ms is possible spin

microstate.

L = 2, ML= , − 1, … . ,0 , … , − , ML = 2, 1, 0, -1, -2 ML is possible

orbital microstate. From the various spin and orbital microstates possible,
a table of all the combined microstates can be generated. The microstates
are the possible orientations of the electron that are allowed by the
Pauling’s and Hund’s rules. A microstate is represented with the orbital
in which the electron is located with superscript representing the spin of
the electron. The total number (N) of microstates for a given d-
( ) !
configuration can be calculated from the expression; N=
!( ( ) )!
where l is electronic orbital angular momentum and x is number of
unpaired electrons. For d1 configuration, l = 2, x = 1 and N =
( ( ) ) !
= 10
!( ( ( ) ) )!

Ms
-1/2 ½

-2 -2- -2+
ML -1 -1- -1+
0 0- 0+
1 1- 1+
2 2- 2+

From the microstates, only 2D term is possible as shown by the coloured

microstates. For d2 and d8 the highest L = 4, ML = 4, 3, 2, 1, 0, -1, -2, -3,
-4. The highest S = 1, MS=1, 0, -1

( ( ) ) !
N= = 45, note that l = 2 and x = 2 for d2 or d8.
!( ( ( ) ) )!

56
CHM 423 MODULE 3

Useful Guide for Microstates’ Representation

i. Ensure that the sum of angular momentum value equals ML for

each row.
ii. Ensure that the sum of spin angular momentum value equals Ms
for each column.
iii. Ensure the arrow corresponds to the spin of the microstate; + (↑)
and – (↓).
iv. Ensure Pauling’s exclusion principle is obeyed; two electrons in
the same orbital must have opposite spins. Such state has no
replicate because both electrons are in the same orbital e. g. +1+
+1- (↑↓) but not +1+ +1+ (↑↑).

MS
-1 0 +1
- ↑ ↓
4 -2+-2-
- ↓ ↑ ↓ ↓ ↑ ↑ ↑
3 ↓ -1+-2- -1--2+ -1+-2+
-1-
-2-
- ↓↓ ↑ ↓ ↓ ↑ ↓ ↑ ↑
2 0-- -2+0- ↑ -1+-1- -2+ 0+
2- -2-0+
- ↓ ↓ ↑ ↓ ↓ ↑ ↑ ↓ ↓ ↑ ↑ ↑ ↑
1 ↓ ↓ -1+ 0- -1- 0+ + -
+1 -2 ↑ -1+ 0+ +1+-
0- -2- +1- 2+
-1- +1 -2+
-

M 0 ↓ ↓ ↑ ↓ ↓ ↑ ↓ ↓ ↑ ↑ ↑ ↑
L ↓ ↓ +2+-2- ↑ +1+-1- ↑ ↓ +2+-2+ ↑
+2 +2-- +1- -
-
+1 - 2+ -1+ 0+0 1++1
- - - +
- 2
1-
1 ↓ ↓ ↑ ↓ ↓ ↑ ↑ ↓ ↓ ↑ ↑ ↑
+ - - + + -
↓ ↓ +1 0 +1 0 -1 +2 ↑ +1+ 0+ ↑
0- +2 -1- -
-
+1 - +2 1++2
-
1- + +

2 ↓ ↑ ↓ ↓ ↑ ↓ ↑ ↑
+ -
↓ +2 0 ↑ +1++1 +2+ 0+
0- - + -
+2 0
+2
-

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CHM 423 COORDINATION CHEMISTRY

3 ↓ ↑ ↓ ↓ ↑ ↑ ↑
↓ +1++2 +1+2 +1++2
- + +
+1
-

+2
-

4 ↑ ↓
+2++2
-

The terms allowed are determined from the table by the numbers of
column(s) and row(s); one column represents singlet spin state, two
represents doublet spin state, three represents triplet spin state and four
quartet spin state. The number of rows represents ML= ±L (atomic orbital
angular momentum):

NO. OF NO. OF ROWS TERM SYMBOL

COLUMNS
3
3 ±3 F
3
3 ±1 P
1
1 ±4 G
1
1 ±2 D
1
1 0 S

After the determination of the allowed term symbols in a free ion, it is

necessary to arrange them in order of stability. The state or term with the
lowest energy (ground term) is determined by considering the following
steps according to Hund’s rule.

1. The state with the highest spin multiplicity is considered most

stable.
2. If there are two or more states with the same multiplicity, the state
with the highest L value is considered most stable.
3. If there are two or more states with the same spin multiplicity and
L value, the state with the lowest J (spin-orbit coupling constant)
will be most stable for d-configuration (d1-d4), while the state with
the highest J will be most stable for d-configuration (d6-d9). An
example using d2 configuration is:

The difference in energy between adjacent levels of J is (J’+ 1)λ, where

J’ is the lower adjacent J value and λ is the spin-orbit coupling constant
e.g. energy difference between 3F2 and 3F3 is (2+1) λ = 3 λ. Under the

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CHM 423 MODULE 3

influence of an external magnetic field, the various J states split into (2J
+ 1) energy levels corresponding to the values the magnetic quantum
number MJ can assume i.e. from J, J-1, ...., -J . The splitting is called
Zeeman Effect. The separation between the levels is given as ρβH where
ρ = Lande’s splitting factor, β = Bohr magneton and H = applied magnetic
field.
( )– ( )
ρ= + ( )

Example; to calculate ρ for 3F2, S = 1, L = 3, J = 2

( )– ( )
ρ= + = 0.50
. ( )

Table below shows the allowed free ion terms for various dn configuration
dn, No. Unpaired Allowed free ion terms
10-n
d electron
1 9 2
d ,d 1 D
d2, d8 2 3
F, 3P, 1G, 1D, 1S
d3, d7 3 4
F, 4P, 2H, 2G, 2F, 2D(2), 2P
d4, d6 4 5
D, 3H, 3G, 3F(2), 3D, 3P(2), 1I, 1G(2), 1D(2),
1
S(2)
5 6
d 5 S, 4G, 4F, 4D, 4P, 2I, 2H, 2G(2), 2F(2), 2D(3),
2
P, 2S

Splitting of Free Ion Terms in Octahedral/Tetrahedral Fields

The crystal field splitting in the tetrahedral field is intrinsically smaller
than in the octahedral field. For most purposes the relationship may be
represented as Δt = 4/9 Δo. Just as the free ions split under the influence
of external magnetic fields, the approach of the ligands also splits the free

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CHM 423 COORDINATION CHEMISTRY

ion terms. The splitting pattern depends on the geometry of the complex.
The spectroscopic states are split into components that have the same
multiplicity as the free ion states from which they arise. A single electron
in a d orbital (d1 and d9) gives rise to a 2D term for the free ion
(uncoordinated), but in an octahedral field, the electron will reside in a
t2gorbital, and the spectroscopic state for the t2g1configuration is 2T2g. If
the electron were excited to an eg orbital, the spectroscopic state would be
2
Eg. Thus, transitions between 2T2g and 2Egstates would not be spin
forbidden because both states are doublets. Note that lowercase letters are
used to describe orbitals, whereas capital letters describe spectroscopic
states.

Term Splitting in Splitting in Total

Octahedral tetrahedral degeneracy
S A1g A1 1
P T1g T1 3
D T2g + Eg T2 + E 5
F A2g + T1g + T2g A2 + T 1 + T 2 7
G A1g + Eg + T2g + T1g A1 + E + T 2 + T 1 9
H Eg + T2g + 2T1g E + T2 + 2T1 11
I A1g + A2g + Eg + 2T2g A1 + A2 + E + 2T2 13
+ T1g + T1

Selection Rule
Spin Rule: states that transitions between states of the same multiplicity
are allowed but transitions between states of different multiplicities are
not allowed. Examples; transitions between 2Tg and 2Eg, 3T1g and 3T2g are
allowed but transitions between 2Tg and 1Eg, 4T1g and 3T2g are not allowed
or they are forbidden.

Larporte Rule: states that transitions between state with ΔL = ±1 are

allowed but those with change in L greater or less than ±1 are forbidden.
This rule implies change in parity or symmetry of orbital; g→g and
u→uare allowed but g→u and u→g are not allowed. s→s, p→p, s→d and
p→fare not allowed but s→p, p→d and d→f are allowed.

Molar Absorptivity (εmax)

The molar absorptivity determines the intensity of a given absorption, a
band with high εmaxwill be intensely coloured while those with low ε max
will not. The value of εmax depends on the transition. Transitions which
are Spin and Larporte allowed have high εmax.

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CHM 423 MODULE 3

Transition εmax (L mol-1cm- Examples

1
)
Spin-forbidden (and Laporte < 1 [Mn(H2O)6]2+, d5
forbidden)

Laporte-forbidden (spin allowed) 20 – 100 [Ti(H2O)6]3+, d1

Laporte-allowed ~ 500 [NiCl4]2-, d8

Symmetry allowed (charge 1000 – 50000 [MnO4]-, d0

transfer)

Transitions in Octahedral Field

d1 and d9 complexes
d1 complex example is [Ti(H2O)6]3+ and d9 complex example is
[Cu(H2O)6]2+, ground term is determined and the split terms arising from
the ground term are arranged based on stability (the number of possible
arrangements in ground state).
Ground term is 2D for d1 and d9
2
D splits into 2Eg and 2T2g for d1 and d9

2
T2g → 2Eg = 20, 300 cm-1 for [Ti(H2O)6]3+
d2 and d8 complexes
d2 complex example is [V(H2O)6]3+ and d8 complex example is
[Ni(H2O)6]2+. Ground term is 3F for d2 and d8 with 3P excited state of same
multiplicity with ground state.
3
F splits into 3A2g, 3T2g and 2T1g while 3P gives rise to 3T1g.

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CHM 423 COORDINATION CHEMISTRY

From the splitting pattern in octahedral field, three transitions are possible
in d2 and d8 complexes. These transitions are observed at specific bands
for individual complexes.

In the spectrum of [V(H2O)6]3+; 3T1g → 3T2g occurs at 17,800cm-1and 3T1g

→ 3T1g (P) occurs at 25,700cm-1. The third transition 3T1g → 3A2g is weak
though of higher energy. In [Ni(H2O)6]2+, the bands are 8500 cm-1 for 3A2g
→ 3T2g 13, 800 cm-1 for 3A2g → 3T1g (F) and 25, 300 cm-1 for 3A2g →
3
T1g (P). Suitable diagrams in which all the various splitting pattern are
well illustrated is established by Orgel.

T1g or T1 A2g or A2

T1g or T 1
T1g or T 1 P
T2g or T2 E g or E
T2g or T2

D
F
T 2g or T 2

Eg or E T2g or T2
T 1g or T1
A2g or A2

d1, d6 Td d1, d6 Oh d2 , d7 Td d2 , d7 Oh
d4, d9 Oh d4, d9 Td d3 , d8 Oh
Td = Tetrahedral d3 , d8 Td
Td = Tetrahedral
Oh = Octahedral Oh = Octahedral

Orgel Diagram for D ground term Orgel Diagram for F ground term with an exicited P term

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CHM 423 MODULE 3

Tanabe-Sugano Diagrams
Orgel diagrams allows a qualitative description of the spin-allowed
electronic transitions expected for states derived from D and F ground
terms while Tanabe-Sugano (TS) diagrams give a semi-quantitative
approach, including both high and low spin ions. TS diagrams cover both
the spin-allowed transitions and the spin-forbidden transitions which are
weak and may not likely be observed. TS diagrams are complex in nature
but a good understanding of the diagrams is very useful in spectra
interpretation. TS diagrams are plots of ratio of energy (E) of transition to
Racah parameter B, (E/B), against ratio of Δ0/B. Different diagrams are
available for different d configurations. The TS diagram d2 is shown in
the figure below.

Tanabe-Sugano diagram for the octahedral d2 case

Application of the Ts Diagram

An aqueous solution of the complex [V(H2O)6]3+ shows two absorption
bands in the region 17, 200 cm-1 and 25, 600 cm-1. These bands have been
assigned to the first two transitions in the complex. For example, with the
aid of TS diagram, calculate the values of Racah parameter B, octahedral
splitting crystal field (Δ0) and the band for the third transition not observed
in the spectrum.

V2+ (d2) has free ion ground term 3F with an excited 3P term of the same
multiplicity. In Octahedral field, the 3F will give 3T1g, 3T2g and 3A2g while
the excited state will give 3T1g. This will give three transitions from the
ground term of 3T1g.

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CHM 423 COORDINATION CHEMISTRY

3
T1g→3T2g energy of transition E1 = 17, 200 cm-1
3
T1g→3T1g (P) energy of transition E2 = 25, 600 cm-1
3
T1g→3A2g energy of transition E3= ?
E/B ratio for the given absorptions E1/B and E2/B
(E2/B)/ (E1/B) = E2/E1 = 25600/17200 = 1.49.

Various points on the Δ0/B axis tried to locate the corresponding values
of E1/B and E2/B that will give the ratio 1.49, from which B can be
calculated.
When Δ0/B = 28. The ratio of (E2/B)/ (E1/B) is 1.49. From the diagram,
the following are obtained E1/B = 25.9, E2/B = 38.6 and E3/B = 53
E1/B = 25.9
17200 cm-1/B =25.9, B = 664 cm-1
E3/B = 53, E3 = 53 X 664 cm-1 = 35, 197 cm-1
Δ0/B = 28, Δ0 = 28 X 664 cm-1 = 18, 592 cm-1

Transitions in Tetrahedral Field

Generally, tetrahedral complexes have more intense absorptions than
octahedral complexes. Tetrahedral complexes are formed with late
transition metal ions (Co2+, Cu2+, Zn2+, Cd2+) and some early transition
metals (Ti4+, Mn2+), especially in situations where the ligands are large.

This is as a result of the absence of a centre of symmetry in tetrahedral

complexes which makes transitions between d orbitals more intense than
in octahedral complexes. From the Orgel diagrams, the d orbitals for
tetrahedral complexes are split in the opposite fashion to octahedral
complexes.

Given any dn configuration, the ground term can be easily determined by

following these steps:

1. Filling the electrons into the five degenerate d-orbitals and

calculate the | L |value for the ground term based on the positions
of the electrons in the orbitals. The filling must follow Hund’s rule
and Pauling Exclusion Principle.
2. The multiplicity is obtained as number of unpaired electrons plus
one (n + 1)

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CHM 423 MODULE 3

Examples:

3.3 Vibrational Spectroscopy

Like the bonds in functional groups of organic compounds, bonds in

inorganic compounds produce infrared spectra that can be used in their
characterisation. Unlike the bonds in functional groups of organic
compounds, the infrared bands for inorganic materials are broader, fewer
in number and appear at lower wave numbers than those observed for
organic materials. If an inorganic compound forms covalent bonds within
an ion: it can give a characteristic infrared spectrum. The bands in the
spectra of ionic or coordination compounds depend on the structures and
orientations of the central metal and the ligands. Generally, complexes
with organic ligands will have characteristic infrared absorption bands of
the functional groups in the ligands. Though as often expected these bands
are expected to shift on coordination especially bands that are
characteristics of the binding site within the organic ligands. The basic
principle of infrared spectroscopy is usually studied in organic chemistry,
but it will be of significance to mention the important aspects of this
principle as it will provide information on why bonds absorb infrared
electromagnetic radiation.

Infrared spectroscopy is an important analytical technique used to study

the nature of bonding in a given chemical compound in order to determine
the various functional groups present therein. This is made possible as
different bonds have different and unique region of infrared absorption.
Infrared spectroscopy is one of the best analytical techniques, as virtually
all forms of samples (including inorganic samples) can be easily studied
and duly investigated. Infrared spectroscopy is based on the vibrations of
the bonds joining atoms together in a molecule. The product of infrared
analysis is the infrared spectrum which is obtained by passing infrared
radiation through a sample and afterward determine what fraction of the
incident radiation is absorbed at a particular energy just like in electronic
spectroscopy. The peaks in the spectrum are characteristics of the
frequencies of absorption of bonds present in the sample analysed. The
spectrum is a plot of percentage transmittance against wave number
expressed in cm-1. With the wave number scale, infrared absorptions for
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CHM 423 COORDINATION CHEMISTRY

all organic compounds (functional groups) occur from 4000 cm–1 to 400
cm–1. However, those of ionic compounds like NaCl and KBr have
absorption bands at higher wavenumber. In complexes, the bonds
between the metal and the binding site in an organic ligand absorb at
lower wavenumber.

Only compounds with dipole moments are capable of absorbing infrared

energy and are said to be infrared active while molecules without dipole
moments are said to be infrared inactive (these group of compounds are
studied using Raman Spectroscopy). Thus, molecules like water,
ammonia are active but molecules like O2, Cl2 are inactive to infrared.
The dipole moment of an infrared-active molecule changes as the bond
expands and contracts. By comparison, an infrared inactive molecule will
have its dipole moment remain zero, no matter how long the bond
vibrates. Coordination compounds are significantly polar; hence, they are
infrared active.

The fundamental modes of vibration in compounds are stretching and

bending. The stretching can be symmetric or asymmetric while the
bending can be wagging, twisting, rocking or deformation. These modes
have different regions of infrared absorption. The energy of the stretching
mode is usually higher than that of bending mode.

Interpretation of Infrared Spectra

After an infrared spectrum has been obtained, it must be interpreted to
determine the functional groups present in the sample. Spectrum is not
complicated like electronic spectrum in ultra violet/ visible spectroscopy.
The various bands in infrared in spectrum have been grouped into what is
known as group frequencies. The characteristic group frequencies are far-
infrared (less than 400cm-1), mid-infrared (400-4000cm-1) and near-
infrared (4000-13,000cm-1) regions.

Far-Infrared Region
The far-infrared region, by definition, has the region between 400 and 100
cm−1. This region is more limited than the mid-infrared for spectra–
structure characterisation. However, it does provide information
regarding the vibrations of molecules of heavy atoms. Intramolecular
stretching modes involving heavy atoms can be helpful for characterising
compounds containing halogen atoms, organometallic compounds and
inorganic compounds.

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CHM 423 MODULE 3

Near-Infrared Region
The absorptions in the near-infrared region (13 000–4000 cm−1) are
usually overtones or combinations of the fundamental stretching bands
which occur in part of the mid-infrared region (3000–1700 cm−1). The
bands involved are usually due to C–H, N–H or O–H stretching. The
resulting bands in the near-infrared are often weak in intensity and the
intensity generally decreases by a factor of 10 between adjacent
successive overtones. The bands in the near-infrared are often overlapped,
making them less useful than the mid-infrared region for qualitative
analysis.

Mid-Infrared Region
The mid-infrared spectrum (4000–400 cm−1) is broadly grouped into four
regions and the character of a group frequency can be determined by the
region in which it is localised. The regions are: the region of absorption
for bond between hydrogen and heteroatom (O–H, C-H, N-H) stretching
region (4000–2500 cm−1), the triple-bonds (C≡N, C≡C) region (2500–
2000 cm−1), the double-bond (C=C, C=N, C=O) region (2000–1500 cm−1)
and the fingerprint (characteristic of the molecule being analysed) region
(1500–600 cm−1). For the fundamental vibrations in the 4000–2500 cm−1
region, O–H stretching gives broad band that occurs in the range 3700–
3600 cm−1. N–H stretching is found in the narrow range 3400-3300 cm−1
with sharper absorption than O–H stretching and can be easily
differentiated, with NH2, resonance occurs and two close sharp bands are
seen instead of one. C–H stretching bands occur at the range 3000–2850
cm−1 in most aliphatic compounds. If the C–H bond is next to a double
bond or aromatic ring, the C–H stretching band occurs between 3100 and
3000 cm−1. Triple-bond stretching absorptions occur in the 2500–2000
cm−1regions due to high force constants of the bonds. C≡C bonds absorb
between 2300 and 2050 cm−1, while the nitrile group (C≡N) occurs
between 2300 and 2200 cm−1. These groups can be easily identified since
C≡C stretching is often very weak, while C≡N stretching is of medium
intensity. These are the most common absorptions in this region, but you
may come across some X–H stretching absorptions, where X is a more
massive atom such as phosphorus or silicon. These absorptions usually
occur near 2400 and 2200 cm−1, respectively.

The major bands in the 2000–1500 cm−1 region are caused by C=C and
C=O stretching. Carbonyl stretching is a very easy absorption to recognise
in this region. It is usually the most intense band in the spectrum. The
nature of C=O bond can also be confirmed as there are regions for various
carbonyl contain organic moieties. It is very germane to know that metal
carbonyls may absorb above 2000 cm−1 C=C stretching is much weaker
and occurs at around 1650 cm−1, but this band is often not observed for
symmetry or dipole moment reasons. C=N stretching also occurs in this
region and is found to be sharper and more intense. The bands in the

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CHM 423 COORDINATION CHEMISTRY

region 1500–650 cm−1 are characteristic of the molecule be analysed

hence region is called the fingerprint region. It is very important to note
that most of the bands may vary from one compound to another and also
from one environment to another. This implies that the values are not
fixed, and in few cases, variation may occur up 100cm-1.

Table of Infrared bands of functional groups

Absorbance Wavenumber, cm-1
O-H stretch of carboxylic 3300-2800 (strong, broad, centers at
acid ~3000)
N-H stretch 3400-3250 (medium intensity, often
broad)
2
sp C-H stretch 3100-3020
3
sp C-H stretch 2960-2850
aldehyde C-H stretch 2830-2695
aromatic overtones 2000-1600
C=O stretch See Table 1
aromatic C=C stretch 1600-1585
alkene C=C stretch 1680-1620
C-O stretch 1150-1050
aromatic ring bends 770-730 and 710-690 (for mono-
substituted ring)

Infrared of Coordination Compounds

Coordination complexes are considered by their structural types and the
vibrational wave numbers of some common functional groups present in
them. Monatomic ligands (halides, oxide and hydride) which coordinate
with metal produce characteristic infrared bands examples; M-X (X=
halides and M= metal) band occurs at 750-100 cm-1, M=O occurs at 1010-
850 cm-1 and M≡N at 1020-875 cm-1. Coordination compounds may also
contain diatomic ligands, in which a metal atom coordinated to molecules
such as CO, NO, O2, N2, H2, OH−or CN−. The wave numbers of such
ligands are shifted to lower regions on coordination due to increase in
bond length.

The absorption bands in coordination compounds depend on the

geometries and the coordination numbers and the donor atoms.
Tetrahedral complexes have two infrared-active modes of vibration;
square planar complexes have three active modes of infrared vibration
while only two are present in octahedral, provided the ligands are
identical. Few examples are presented below:

Complex Geometry Bands (cm-1)

[PtCl4]2- Square planar 147, 313, 165
[PdCl4]2- Square planar 150, 321, 161
[MnO4]- Tetrahedral 902, 386
68
CHM 423 MODULE 3

[CrO4]- Tetrahedral 890, 378

[PtCl6]2- Octahedral 343, 183
[VCl6]2- Octahedral 646, 300

There are however many complexes with complicated IR spectra.

Generally, Metal complexes or chelates are largely covalent in nature and
the spectra of such compounds are overwhelmed by the contribution of
the ligand and its coordination modes. The ligands may be small species,
such as water, ammonia, CO or phosphine or as large as porphyrin.

Infrared spectra can help to identify linkage isomers as there are

differences in characteristic absorptions of the isomers. Linkage
isomerism occurs when a ligand has the ability to coordinate to a central
metal using either of two atoms within the ligand. The nitrite ion exhibits
this type of isomerism. When the nitrite ion is attached to a central metal
ion via the nitrogen atom, it is known as a nitro ligand. When one of the
oxygen atoms is the donor, it is known as a nitrito ligand. When NO2-
bonds undergo bonding through an oxygen bond, one of the NO bonds is
‘nearly’ a double bond, while the other is a single bond. In the other
coordination, both NO bonds are intermediate between single and double
bonds. The infrared band of a bond increases as its strength increases and
so it would be expected that the wavenumbers of the NO bonds in
NO2−increase in the order: single-bond NO (in O-bonded) <NO (in N-
bonded) <double-bond NO (in O-bonded). It is observed that in
complexes when NO2−is bonded through oxygen, N=O stretching appears
in the 1500–1400 cm−1 range while N–O stretching appears at 1100–1000
cm−1. In complexes in which NO2−is bonded through nitrogen, the
infrared bands appear at 1340–1300 cm−1 and 1430–1360 cm−1, which are
intermediate values when compared to the oxygen-bonded complex. This
indicates that it is possible to use infrared spectroscopy to determine
whether a nitrite is coordinated and whether it is coordinated through a
nitrogen or oxygen atom.

3.4 Magnetic Measurements

Movement of electrical charge generates magnetic field in any material.

Magnetism is therefore a characteristic property of all materials that
contain electrically charged particles that are in continuous motion and
for most purposes can be considered to be entirely of electronic origin. In
an atom, the magnetic field is due to the coupled spin and orbitalmagnetic
moments associated with the motion of electrons. The spin magnetic
moment is due to the precession of the electrons about their own axes
whereas the orbital magneticmoment is due to the motion of electrons
around the nucleus. The resultant combination of the spin and orbital
magnetic moments of the constituent atoms of a material gives rise to
theobserved magnetic properties. Many transition metal compounds are

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CHM 423 COORDINATION CHEMISTRY

paramagnetic due to the presence of unpaired electrons. Magnetic

moment of each electron is associated with its spin angular momentum
and orbital angular momentum.

Principle of Magnetism
According to Lenz's Law, which states that when a substance is placed
within a magnetic field, H, the field within the substance, B, differs from
H by the induced field, which is proportional to the intensity of
magnetisation (I).

It can be mathematically expressed as B = H + 4 I, where B is the

magnetic field within the substance, H is the applied magnetic field and
Iis the intensity of magnetisation. By dividing through with H, It can also
be expressed as;

B/H = 1 + 4 I/H, or P = 1 + 4
where B/H is called the magnetic permeability (P) of the material and
is the magnetic susceptibility per unit volume, (I/H). By definition, K
in a vacuum is zero, where B = H. Note that P = B/H = 1
It is usually more convenient to measure mass than volume and the mass
susceptibility, , is related to the volume susceptibility, , through the
density.
χg = K/d where d is the density.

It is necessary to measure this quantity on the basis that can be related to

atomic properties, it is therefore converted to molar susceptibility by
multiplying the mass susceptibility with relative molar mass (RMM) of
the atom.

χm =χg * RMM
All materials are known to have inherent diamagnetism, it is important to
include a term that will reflect this diamagnetism of the material being
measured to have a corrected molar susceptibility.

χcorr = χm + χdia
Curies Law is obeyed by Normal paramagnetic substances
χm = C/T

where C is the Curie constant. A plot of 1/Χ versus T should give a

straight line with the slope 1/C passing through the origin (0 K). Some
substances give a straight line that intercepts just a little above or below
0K and these are said to obey the Curie-Weiss Law:
χ = C/(T ± φ)where φ is known as the Weiss constant.

The constant C is given by the Langevin expression which relates the

susceptibility to the magnetic moment;

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CHM 423 MODULE 3

m = Nμ2/3kT
where N is Avogadro's number, k is the Boltzmann constant and T the
absolute temperature.

μ = 2.828 .
Based on quantum mechanics, the magnetic moment is dependent on both
spin and orbital angular momentum contributions. The spin-only (s.o.)
formula is expressed as
μs.o. = 4 ( + 1) or μs.o. = ( + 2)

where S is the resultant spin angular momentum and n is the number of

unpaired electrons. This expression can be modified to include orbital
contribution to the magnetic moment.
μ = (4 ( + 1) + ( + 1))

Types of Magnetic Behaviours

Diamagnetism
Diamagnetism is a phenomenon in some materials in which the
susceptibility is negative (χm), i.e. the induced magnetism opposed the
applied field. It arises from the precession of spinning charges in a
magnetic field. The magnetisation is in the opposite direction to that of
the applied field, i.e. the magnetic susceptibility is negative (χm< 0).
Although all substances are diamagnetic, it is a weak form of magnetism
and may be masked by other, stronger forms. Diamagnetism results from
changes induced in the orbits of electrons in the atoms of a substance by
the applied field, the direction of change (in accordance with Lenz's law)
opposing the applied magnetic flux. There is thus a weak negative
susceptibility (χm< 0).

Diamagnetism is a very weak form of magnetism that is only exhibited in

the presence of an external magnetic field. It is the result of changes in
the orbital motion of electrons due to the external magnetic field. The
induced magnetic moment is very small and in a direction opposite to that
of the applied field. When placed between the poles of a strong
electromagnet, diamagnetic materials are attracted towards regions where
the magnetic field is weak. Diamagnetism is found in all materials;
however, because it is so weak it can only be observed in materials that
do not exhibit other forms of magnetism. Also, diamagnetism is found in
elements with paired electrons. Complexes without unpaired electrons are
diamagnetic in nature; this is a characteristic of d0 and d10 complexes with
other d configuration with no unpaired electrons.

Paramagnetism
In paramagnetism, the atoms or molecules of the substance have net
orbital or spin magnetic moments that are capable of being aligned in the

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CHM 423 COORDINATION CHEMISTRY

direction of the applied field. They possess positive magnetic

susceptibility (χm). Paramagnetism occurs in all substances with unpaired
electrons; e.g. free atoms, free radicals, and complexes of transition
metals containing ions with partially filled d orbitals. It also occurs in
metals as a result of the magnetic moments associated with the spins of
the conducting electrons.

Paramagnetism is the tendency of the atomic magnetic dipoles, due to

quantum-mechanical spin angular momentum, in a material that is
otherwise non-magnetic to align with an external magnetic field. This
alignment of the atomic dipoles with the magnetic field tends to
strengthen it, and is described by magnetic permeability greater than unity
or equivalently a positive magnetic susceptibility above zero.

In pure paramagnetism, the external magnetic field acts on each atomic

dipole independently and there are no interactions between individual
atomic dipoles. Such paramagnetic behaviour can also be observed in
ferromagnetic materials that are above their Curie temperature.
Paramagnetic materials attract and repel like normal magnets when
subject to a magnetic field. Under relatively low magnetic field saturation
when the majority of the atomic dipoles are not aligned with the field,
paramagnetic materials exhibit magnetisation according to Curie’s law;
χm = C/T

The law shows that paramagnetic material becomes less magnetic as

temperature is increased. Paramagnetic materials in magnetic fields will
act like magnets but when the field is removed, thermal motion will
quickly disrupt the magnetic alignment. In general, paramagnetic effects
are small (magnetic susceptibility of the order of χm ~ 10-3 to 10-5).
Ferromagnetic materials above the Curie temperature become
paramagnetic.

Ferromagnetism
When the centres of paramagnetic species are very close, a magnetically
ordered material in which there is a bulk magnetic moment with large
magnetisation is obtained. The electron spins of the atoms in the
microscopic regions, domains, are aligned. In the presence of an external
magnetic field the domains oriented favourably with respect to the field
at the expense of the others and the magnetisation of the domains tends to
align with the field. This phenomenon is called Ferromagnetism. Above
the Curie temperature, the thermal motion is sufficient to offset the
aligning force and the material becomes paramagnetic. Certain elements
(iron, nickel and cobalt), and alloys with other elements (titanium,
aluminium) exhibit relative magnetic permeabilities up to 104
(ferromagnetic materials). Below a certain temperature, called the Curie
point (or Curie temperature) an increasing magnetic field applied to a

72
CHM 423 MODULE 3

ferromagnetic substance will cause increasing magnetisation to a high

value called the saturation magnetisation. This is because a ferromagnetic
substance consists of small magnetised regions called domains. The total
magnetic moment of a sample of the substance is the vector sum of the
magnetic moments of the component domains. Ferromagnetic materials
obey the Curie-Weiss Law:
χ = C/(T+φ)

Antiferromagnetism
This is a phenomenon in some magnetically ordered materials in which
there is an anti-parallel alignment of spins in two or more close centres of
paramagnetic structures so that there is overall cancellation of bulk
spontaneous magnetisation. In antiferromagnetic materials, the condition
is such that the spins aligned in a manner in which they cancelled out the
overall magnetisation. Antiferromagnetism results in the spins of
magnetic electrons align in a regular pattern with neighbouring spins
pointing in opposite directions. This is the opposite of ferromagnetism.
Generally, antiferromagnetic materials exhibit antiferromagnetism at a
low temperature, and become disordered above a certain temperature; the
transition temperature is called the Néel temperature. Above the Néel
temperature, the material is typically paramagnetic. The
antiferromagnetic behaviour at low temperature usually results in
diamagnetic properties, but can sometimes display ferromagnetic (where
some spins are not cancelled out) behaviour, which in many physically
observable properties are more similar to ferromagnetic interactions.
The magnetic susceptibility, χm of an antiferromagnetic material will
appear to go through a maximum as the temperature is lowered; in
contrast, that of a paramagnet will continually increase with decreasing
temperature. Antiferromagnetic materials have a negative coupling
between adjacent moments and low frustration. Antiferromagnetic
materials are relatively uncommon. There are also numerous examples
among high nuclearity metal clusters.
χ = C/(T - φ)

Ferrimagnetism is a property exhibited by materials whose atoms or ions

tend to assume an ordered but nonparallel arrangement in zero applied
field below a certain characteristic temperature known as the Néel
temperature. In the usual case, within a magnetic domain, a substantial
net magnetisation results from the antiparallel alignment of neighbouring
non-equivalent sublattices. The macroscopic behaviour is similar to
ferromagnetism. Above the Néel temperature, these substances become
paramagnetic.

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CHM 423 COORDINATION CHEMISTRY

1/X
sm
neti
ag

ism
m

et sm
ro

n eti
er

ag n
ti f

ra
m ag
an

a m
p rro
fe

TN 0 Tc T(k)

Tc: ferromagnetic Curie temperature (below Tc, sample is ferromagnetic)

TN: Néel Temperature (below TN, sample is antiferromagnetic)

Orbital Contribution to Magnetic Moment in Paramagnetic

Complexes

T Ground Term
An orbital angular momentum contribution is expected when the ground
term is triply degenerate i.e. a T state such T1 or T2 in both tetrahedral and
octahedral fields. Octahedral complexes where the triply degenerate (dxy,
dyz and dxz) orbitals are not equally (such as d1, d2, d4 and d5 low spins)
will have orbital contribution to magnetic moment. This implies that the
experimental magnetic moment μeff will be greater than the μs.o. These
complexes will also show temperature dependence in magnetic moment
as well.

74
CHM 423 MODULE 3

In order for an electron to contribute to the orbital angular momentum the

orbital in which it resides must be able to transform into an exactly
identical and degenerate orbital by a simple rotation (it is the rotation of
the electrons which induces the orbital contribution). For example, in an
octahedral complex the degenerate t2g set of orbitals (dxz,dyx,dyz) can be
interconverted by a 90o rotation. However the orbitals in the eg subset
(dz2,dx2-y2) cannot be interconverted by rotation about any axis as the
orbital shapes are different; therefore an electron in the eg set does not
contribute to the orbital angular momentum and is said to be quenched.
In the free ion case, the electrons can be transformed between any of the
orbitals as they are all degenerate, but there will still be partial orbital
quenching as the orbitals are not identical. Electrons in the t2g set do not
always contribute to the orbital angular moment. For example in the d3,
t2g3 case, an electron in the dxz orbital cannot by rotation be placed in the
dyz orbital as the orbital already has an electron of the same spin. This
process is also called quenching.

Tetrahedral complexes can be treated in a similar way with the exception

that we fill the e orbitals first, and the electrons in these do not contribute
to the orbital angular momentum. Tetrahedral complexes of d3, d4, d8 and
d9 are going to experience orbital contribution to magnetic moment.

Configurations corresponding to the T2 term (from D) or a T1 term (from

an F term) have direct contribution to orbital angular momentum. The
magnetic moments of complexes with T terms are often found to show
considerable temperature dependence. This is as a result of spin-orbit
coupling that produces levels whose energy differences are frequently of
the order kT, so as a result, temperature will have a direct effect on the
population of the levels arising in the magnetic field.

A2 or E Ground Term
The configurations corresponding to the A1 (free ion S term), E (free ion
D term), or A2 (from F term) do not have a direct contribute to the orbital
angular momentum. For the A2 and E terms there is always a higher T
term of the same multiplicity as the ground term which can affect the
magnetic moment (usually by a only small amount).

μeff = μs.o (1- αλ/Δ)

where α is a constant (2 for an E term, 4 for an A2 term) λ is the spin-orbit
coupling constant which although generally not available does give
important information since the sign of the value varies depending on the
orbital occupancy. For d1 to d4 the value is positive hence μeff is less than
μs.o while for d6 to d9 the value is negative hence μeff is greater than μs.o. Δ
is the crystal field splitting factor for complexes.

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CHM 423 COORDINATION CHEMISTRY

Table showing octahedral dn and possibility of orbital contribution (OC)

to magnetic moment

Ion dn Config. Free Ground O. μs.o μobs μL +S

ion term C. (BM) (BM) (BM)
term
Ti3+ d1 t2g1 2
D 2
T2g Yes 1.73 1.6- 3.00
1.7
V3+ d2 t2g2 3
F 3
T1g Yes 2.83 2.7- 4.47
2.9
V2+ d3 t2g3 4
F 4
A2g No 3.88 3.8- 5.20
3.9
Cr2+ d4 t2g3 eg1 5
D 5
Eg No 4.90 4.7- 5.48
HS 4.9
Cr2+ d4 t2g4 3
F 3
T1g Yes 2.83 3.2- 4.47
LS 3.3
Mn2+ d5 t2g3 eg2 6
S 6
A1g No 5.92 5.6- 5.92
HS 6.1
Mn2+ d5 t2g5 2
D 3
T2g Yes 1.73 1.8-
LS 2.1
Fe2+ d6 t2g4 eg2 5
D 5
T2g Yes 4.9 5.1- 5.48
HS 5.7
Fe2+ d6 t2g6 1
S 1
A1g No 0 0
LS
Co2+ d7 t2g5 eg2 4
F 4
T1g Yes 3.88 4.3- 5.20
HS 5.2
Co2+ d7 t2g6 eg1 2
D 2
Eg No 1.73 1.8
LS
Ni2+ d8 t2g6 eg2 3
F 3
A2g No 2.82 2.9- 4.47
3.3
Cu2+ d9 t2g6 eg3 2
D 2
Eg No 1.73 1.7- 3.00
2.2

Table showing Tetrahedral dn and possibility of orbital contribution (OC)

to magnetic moment
Ion dn Config. Free ion Ground O. C. μs.o μobs
term term (BM) (BM)
5+ 1 1 2 2
Cr d e D E No 1.73 1.7-1.8
4+ 2 2 3 3
Cr d e F A2 No 2.83 2.8
5+ 3 2 1 4 4
Fe d e t F Ti No 3.88 3.6-3.7
Mn2+ d5 e2 t23 6
S 6
A1 No 5.92 5.9-6.2
2+ 6 3 3 5 5
Fe D et D E No 4.9 5.3-5.5
2+ 7 4 3 4 2
Co d e t2 F A2 No 3.88 4.2-4.8
2+ 8 4 4 3 3
Ni d e t2 F T1 No 2.83 3.7-4.0

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CHM 423 MODULE 3

Example:
Account for the magnetic moments of the complex, [NiCl4]2- recorded at
80, 99 and 300 K.
80K 99K 300K
3.24 3.42 3.89 B.M.
Ni2+ (d8).

The formula suggests a 4-coordinate complex and it can be assumed that

the complex is tetrahedral with a d electron configuration of e4 t24
therefore the spin-only magnetic moment is 2.83 BM.

From the table above, the ground term is 3T1 therefore, orbital contribution
is going to influence the magnetic moment which must also be
temperature dependent. It is necessary to include the orbital terms in
estimating the magnetic moment. S = 1 and L = 3.

μ= (4 ( + 1) + ( + 1)) = √20 = 4.47 BM

The value obtained is in between the room temperature magnetic moment

and the spin only value. The difference between μL+ S and μobs may be
attributed to partial quenching of the orbital contribution to magnetic
moment.

Example:
At 300 K, the observed value of μeff for [V(NH3)6]Cl2 is 3.9 BM. Confirm
that this corresponds to what is expected for an octahedral d3 complex.
n = 3 and S = 3(1/2) ,μs.o. = 4 ( + 1) or μs.o. = ( + 2)
μs.o. = 4 ( + 1) = 4(3/2)(3/2 + 1) = 3.9 BM or μs.o. =
3(3 + 2) = 3.9 BM

Example:
Given that ∆0 is 10,800 cm-1 and = -315 for the complex [Ni(NH3)6]2+,
determine the μeff and compare the result with μs.o and μS + L. Comment on
the values.
Ni2+ has d8configuration and 3F free ion ground term, which will give rise
to 3A2g in octahedral field. Since there exist a triple degenerate excited
term, orbital contribution is expected. Note that α = 4 for A 2 term,
μs.o=2.83 BM and μS+ L = 4.47 BM

μeff = μs.o (1- αλ/Δ) = 2.83(1 – 4(-315/10,800)) = 3.16 BM

The result of the calculation shows that there is orbital contribution to

magnetic moment due to excited T term the contribution is however very
small as the estimated value is less than 4.47 BM expected with a T
ground term but consistent with experimental value of 3.16 BM reported
for similar Ni2+ complex.

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CHM 423 COORDINATION CHEMISTRY

SELF ASSESSMENT EXERCISE

i. Calculate the total number (N) of microstates for d2 configuration

ii. Calculate spin-only magnetic moment of [V(NH3)6]2 at 300K
iii. Itemize different types of magnetic behaviours
iv. Copy and complete the Table below:
v. Determine the spin state of the complex [Cr(NH3)6]Cl2 given that
its μeff is 4.85 BM at 298K
vi. State Larporte’s rule

4.0 CONCLUSION

The magnetic, electronic absorption and vibrational properties of

complexes have been discussed and it is expected that you should be able
to apply the principles of electronic absorption and vibration to interpret
the spectra of octahedral and tetrahedral complexes. With knowledge of
infrared spectroscopy, linkage isomers can be easily distinguished. The
electronic spectra interpretation helps to determine the energy of
transition between split d orbitals in a complex. The magnetic moment
can be used to identify the spin state of complexes.

5.0 SUMMARY

In this unit, you learnt the following:

 The electronic absorption spectra of complexes have been

interpreted using Orgel diagrams and Tanabe-Sugano diagrams.
 The magnetic moments of complexes have been calculated based
on spin angular momentum and a combination of spin and orbital
angular momenta.
 The results of room temperature magnetic moment of complexes
have been interpreted based on possible orbital contributions as
observed in some complexes.
 The four basic forms of magnetisms adopted by complexes
(paramagnetism, diamagnetism, ferromagnetism,
antiferromagnetism) have been discussed.
 Curie’s law and curie-Weiss laws have been used to describe the
forms of magnetism and their temperature dependence as observed
in complexes.
 The principle and application of infrared vibrational spectroscopy
in structural determination of complexes have been discussed.

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CHM 423 MODULE 3

6.0 TUTOR-MARKED ASSIGNMENT

1. For the following high spin ions, describe the nature of the possible
electronic transitions and give them in the order of increasing
energy. (Time allowed: 10 mins)
2. Given that ∆0 is 8, 500 cm-1 and = -315 for the complex
2+
[Ni(H2O)6] , determine the μeff and compare the result with μs.o
and μS + L. Comment on the values. (Time allowed: 7 mins)
3. Determine the ground term for the following and predict the most
likely value of effective magnetic moments of the following
complexes. State the possibility of orbital contribution where
appropriate. (Time
allowed: 15 mins)
4. Interpret the following room temperature (300K) magnetic
moments.
(i) Fe(acac)3 5.92BM
(ii) Mn(acac)3 4.86BM
(iii) BaMnF6 3.80BM
(iv) Cs2CoCl4 4.71BM
(v) K2Cu(SO4)2.6H2O 1.91BM
(vi) [Cr(en)3]I3.H2O 3.93BM
(vii) VCl41.69BM
(viii) K4[Mn(oxalate)3].3H2O 3.18BM
(ix) [Ni(NH3)6]Cl2 3.11BM
(x) [Cu(NH3)4](NO3)2 1.89BM.
(Time allowed: 25 mins)

5. The absorbance of a 0.1 M aqueous solution of [Ti(H2O)6]3+ was

found to be 0.56 when measured in a 1 cm cuvette. A distorted
absorption band was centered at 20,300cm-1. Account for the
spectrum and calculate the molar absorbance (ε). What would be
the absorbance of the same solution in a 2 cm cuvette? (Time
allowed: 10 mins)
6. The electronic absorption spectrum of [Ni(H2O)6]2+ shows three
bands at 8,500, 15,400 and 26,000 cm-1. Account for these bands
using an Orgel diagram. (Time allowed: 5 mins)

7.0 REFERENCES/FURTHER READING

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rd ed.). Interscience Publishers, division of John Wiley & Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

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CHM 423 COORDINATION CHEMISTRY

Figgis, B. N. & Hitchman, M. A. (2000). Ligand Field Theory and Its

Applications. New York: Wiley.

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry (2nd ed.).

Pearson Education Limited.

Miessler, G. L. & Tarr, D. A. (2010). Inorganic Chemistry (3rd ed.).

Pearson Education Int.

Kettle, S. F. A. (1998). Physical Inorganic Chemistry: A Coordination

Approach. New York: Oxford University Press.

Porterfield, W. W. (1993). Inorganic Chemistry: A Unified Approach,

(2nd ed.). San Diego, CA.: Academic Press.

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CHM 423 MODULE 4

MODULE 4

UNIT 1 THERMODYNAMIC STABILITY AND

REACTION OF COMPLEX

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Thermodynamic Stability of Complex Compound
3.2 The Chelate Effect
3.3 Kinetics and Mechanism of Complexes
3.4 Reaction Mechanism in Complexes
3.5 In-Text Questions and Answers
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

When the term stability is applied to coordination compounds (metal

complexes) there can be two interpretations: thermodynamic or kinetic
stability. Thermodynamic stability refers to the change in energy on going
from reactants to products, i.e., ∆G for the reaction. Recall that ∆G = ∆H-
T∆S = -RT lnK, where ∆H is the enthalpy, ∆S the entropy and K is the
equilibrium constant for the reaction. Kinetic stability refers to reactivity,
generally, ligand substitution which occurs extremely rapidly in some
cases and extremely slowly in others. Thermodynamic stability and
reaction kinetics of coordination compound is a very important aspect of
coordination chemistry and its application cut across all disciplines some
of which are; catalyst design in production industries, pharmaceutical
studies of drug design, chemical analysis and biochemical studies of drug
metabolism. This is because the stability study and reaction mechanism
of complexes determine their behaviour in different environments that
may include change in temperature or change in pH of reaction medium.
It is important to know that there is a line of separation between kinetic
and thermodynamic stability of complexes as sometime the two terms are
without conveying their real meaning. Thermodynamic stability is a
function of the equilibrium constant. Higher equilibrium constant
indicates greater stability of a complex. However, kinetics is a function
of the rate constant. The reaction with high rate constant is expected to
proceed fast.

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2.0 OBJECTIVES

By the end of this unit, you should be able to:

 explain the fundamental difference between reaction

thermodynamic and Kinetics
 write chemical equilibrium expression and determine step-wise
stability constant and overall stability constant of complexes
 estimate and interpret the entropy and free energy of complexes
 explain reaction mechanism in complexes.

3.0 MAIN CONTENT

3.1 Thermodynamic Stability of Complex Compounds

A metal ion in solution exists in complex form, in combination with

ligands (such as solvent molecules or simple ions) or chelating groups.
Thermodynamic stability often refers to the energetics and associated
equilibrium constant for the reaction of an aquated metal ion with some
other ligand (other than water). As noted earlier, complexes may be
neutral or cationic or anionic, depending on the charges carried by the
central metal ion and the coordinated groups. Stability of a complex in
solution refers to the degree of association between the two species
involved in a state of equilibrium. Qualitatively, the greater the
association, the greater is the stability of the compound. The magnitude
of the equilibrium stability constant for the association, quantitatively
determines the stability.

Thermodynamic stability of a complex is a measure of the extent to which

this complex will be formed or be transformed into another complex
under stated conditions on reaching equilibrium. If only soluble
mononuclear complexes are formed in a solution containing metal ion,
Mn+, and monodentate neutral ligand, the system at equilibrium can be
described by the following expression;

[M]n+ + L⇌ [ML]n+ K1 = {[ML] n+} / {[M] n+}[L]

[ML]n++ L ⇌ [ML2]n+ K2 = {[ML2]n+}/ {[ML] n+}[L]
[ML2]n+ + L ⇌ [ML3]n+ K3 = {[ML3]n+}/ {[ML2] n+}[L]
[ML3]n+ + L ⇌ [ML4]n+ K4 = {[ML4]n+}/ {[ML3] n+}[L]

The reaction will proceed till a certain coordination number (N) is attained
[MLN-1]n+ + L ⇌ [MLN]n+ KN = {[MLN]n+}/ {[MLN-1] n+}[L]
The equilibrium constants K1, K2, K3, K4....... and KN are called stepwise
formation or stability constants. When combined together, the overall
formation constant (βN) is derived

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βN = K1 x K2 x K3 x K4........ KN or log βN = log K1 + log K2 + log K3

+ log K4 +..... log KN

In most cases, the value of stepwise formation constant decreases as the

coordination number increases. Example is the reaction between aqueous
solution of Cd2+ and NH3

βN = K1 × K2 × K3 × K4 = 102.65 + 2.10 + 1.44 + 0.93 = 107.12 OR Log βN = 7.12

Reasons for the decrease in the K value are statistical factors, increased
steric hindrance when the incoming ligand is larger than the leaving
ligand and the columbic force of the ligand is charged. Provided known
concentrations of metal ion and ligand react together to give a complex
whose composition is known, the stability constant can be determined for
such reaction by measuring the concentration of the unreacted ligand,
metal ion or the complex formed. This can be achieved by monitoring
change in one of the properties of a component in the system or use of pH
measurement, ion-exchange, electronic or NMR techniques.

Example: The aqueous substitution reaction of Ni2+ with NH3 is study at

300 K using pH measurement. The stepwise formation constants for the
various steps in the reaction are K1 = 102.79, K2 = 102.26, K3 = 101.69, K4 =
101.25, K5 = 100.74, K6 = 100.03 determine the overall formation constant,
the free energy (ΔG) at 300 K and entropy (Δ ), given that change in
enthalpy (ΔH) is -60.28kJ/mol and gas constant (R) = 8.314J/(K.mol).

β6 = K1 xK2 x K3 x K4 x K5 x K6 =108.76
ΔG = - RTln β6 = -8.314 x 300 x ln 108.76 = -50.31kJ/mol
ΔS = (ΔH – ΔG)/T = (-60.28-(-50.31))/300 = 33.23J/(K.mol)

3.2 The Chelate Effect

Chelation is a type of bonding of ions and molecules to metal ions. It

involves the formation or presence of two or more separate coordinate
bonds between a polydentate (multiple bonded) ligand and a single central
atom. These ligands are called chelants, chelators, chelating agents, or
sequestering agents. The term chelate effect is used to describe special
stability associated with complexes containing chelate ring when
compared to the stability of related complexes with monodentate ligands.
The chelate effect can be seen by comparing the reaction of a chelating

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ligand and a metal ion with the corresponding reaction involving

comparable monodentate ligands. For example, comparison of the
binding of 2,2'-bipyridine with pyridine or 1,2 diaminoethane
(ethylenediamine = en) with ammonia.

It has been established for many years that keeping the coordination
number of the metal ion same, the complex resulting from coordination
with the chelating ligand is much more thermodynamically stable as
compared to that formed with monodentate ligand. This can be
established from the stability constant of the complexes formed adding
two monodentate ligands compared with adding one
didentate/bidentateligands, or adding four monodentates compared to two
didentates, or adding six monodentates compared to three didentates. The
complex formation of Ni2+ with ammonia or 1,2-diaminoethane, can be
expressed by the following equations:

[Ni(H2O)6]2+ + 6NH3 → [Ni(NH3)6]2+ + 6H2O β6 = 108.76

[Ni(H2O)6]2+ + 3en → [Ni(en)]2+ + 6H2O β6 = 1018.28

The overall stability constant value for the Ni2+ complex with three
chelate rings (en) is about 1010 greater than that formed with six
monodentate ligands (NH3). This greater stability for complexes of
chelate complexes is termed the chelate effect. Its origin is primarily in
the differences in entropy between chelate and non-chelate complex
reactions. Thus, major factors responsible for the special stability of
chelate can be attributed to increase in entropy as the reaction leading to
the formation of the chelate results in increase in pollution of product
species when compared to reactant species. However, with monodentate
ligand, the reaction results in no change in population. The formation of
chelate complexes results in greater disorder because of the formation of
a larger number of free particles in the products whereas there is no
change in the number of particles in the formation of comparable
nonchelated complexes.

Another factor could be based on the understanding of how the reactions

might proceed. Formation of a complex with 6 monodentate ligands
requires 6 separate favourable collisions between the metal ion and the
ligand molecules. On the contrary, the tris-bidentate metal complex
requires an initial collision for the first ligand to attach by one arm, the
other arm is always going to be nearby and only requires a rotation of the
other end to enable the ligand to form the chelate ring. Thus, in the process
of dissociation, when a monodentate group is displaced, it is lost into the
bulk of the solution. On the other hand, if one end of a bidentate group is
displaced the other arm is still attached and it is only a matter of the arm
rotating around and it can be reattached again. These conditions favour

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the formation of the complex with bidentate ligands rather than

monodentate ligands.

One ligand that forms very stable complexes is the anion

ethylenediaminetetraacetate (EDTA4-). This ion can bond at six sites, so
one EDTA4- ion replaces six water molecules when the reaction is carried
out in aqueous solution. The result is the formation of complexes that have
very high stability constants. This ligand is widely used in analytical
chemistry in complexiometric titrations to determine concentrations of
metal ions. Because it holds metal ions so securely, EDTA4- (in the form
of Na4EDTA, Na2CaEDTA, or Ca2EDTA) is added to salad dressings.
Traces of metal ions catalyse oxidation reactions that lead to spoilage, but
when EDTA4- is added, it binds to the metal ions so effectively that they
cannot act as catalysts for the undesirable oxidation reactions. Many metal
ions are effectively complexed (or sequestered) by EDTA4- or H2EDTA2-
, including main-group ions such as Mg2+, Ca2+ and Ba2+.

It is not only the formation of chelate rings that influences the stability of
complexes, but also ring size is important. Studies have shown that
chelate rings having five or six members are generally more stable than
those of other sizes. For example, when the series of ligands having the
formula H2N(CH2)nNH2 (where n = 2, 3, or 4) forms complexes with the
same metal ion, the most stable complex is with ethylenediamine ( n = 2),
which results in a 5-membered chelate ring. If n = 3, which corresponds
to 1, 3-diaminopropane, the complexes formed have 6-membered rings
and are less stable than are those of ethylenediamine. The complexes with
the ligand having n = 4 (1,4-diaminobutane) are even less stable. A similar
situation exists for complexes of the anions of dicarboxylic acids, -OOC-
(CH2)n-COO- (where n = 0, 1, …).

N N
N

M M
M
N N N

Decrease in stability with increase in ring size

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CHM 423 COORDINATION CHEMISTRY

3.3 Kinetics and Mechanisms of Complexes

Kinetics of complex reaction is the speed at which transformations
leading to attainment of equilibrium will occur. Most often, complexes
undergo reaction in which composition of their coordination sphere
change by substitution of one ligand by another. The process by which
this substitution occurs in complex reactions is referred to as lability.
Complex that undergo lability very fast are said to be labile while others
that undergo similar reaction at slow rate are called inert. It is important
to note that, a complex can be inert and yet be thermodynamically
unstable. Typical example is [Co(NH3)6]3+ which will persists for days in
acid medium but yet unstable thermodynamically. On the other hand,
[Fe(H2O)5F]2+ is labile and yet thermodynamically stable. Complexes of
d3, low spin d4, d5 and d6 as well as d8 square planar are chemically inert.
Complexes of d1, d2 high spin d4, d5 and d6 as well as d7, d9 and d10 are
labile.

Kinetic Study
Kinetic study can be carried out with different forms of techniques
depending on the rate of the reaction to be studied. Experimental
techniques have been developed to monitor reactions over time scales
varying from as low as 10-15s to hours or days. While it is relatively simple
to monitor the kinetics of a slow reaction occurring in few minutes or
hours, highly specialised techniques are required in order to study fast
reactions.

Generally, kinetics study involves techniques essentially consists of

mixing the reactants and initiating reaction on a time scale that is
negligible relative to that of the reaction, and then monitoring the
concentration(s) of one or more reactants and/or products as a function of
time. Because rate constants vary with temperature, it is also important to
determine and control accurately the temperature at which the reaction
occurs. The techniques generally used to study reaction kinetics can be
grouped into;

1. Static methods (for reaction with half-life greater than one minute)
2. Flow or rapid mixing techniques (1 min.≥ half -life ≥ 10-3 sec.)
3. Relaxation methods (when half-life is less than 10-1 sec.)

Static Methods of Kinetic Study

Static methods are used for studying inert reactions which occur over
minutes to hours. The reaction is usually initiated simply by mixing the
reactants together by hand or with a magnetic stirrer or other mechanical
device and the progress of the reaction can be monitored over a time frame
by observing a change in physical or chemical properties of one of the
reactants or product. Colour change, pH change, gas evolution, isotopic
exchange can be the changes being observed.

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CHM 423 MODULE 4

Flow or Rapid Mixing Techniques of Kinetic Study

Flow techniques are used to study reactions occurring on timescales of
seconds to milliseconds. In the simplest flow method, reactants are mixed
at one end of a flow tube, and the composition of the reaction mixture is
monitored at one or more positions further along the tube. If the flow
velocity along the tube is known, then measurements at different positions
provide information on concentrations at different times after initiation of
reaction. The progress of the reaction can be monitored using physical
and chemical changes mentioned in static methods.

Continuous flow methods have the disadvantages that relatively large

quantities of reactants are needed, and very high flow velocities are
required in order to study fast reactions. These problems may be avoided
by using a stopped flow technique. In this method, a fixed volume of
reactants are rapidly flowed into a reaction chamber and mixed by the
action of a syringe fitted with an end stop. The composition of the reaction
mixture is then monitored spectroscopically as a function of time after
mixing at a fixed position in the reaction chamber.

Relaxation Methods of Kinetic Study

These methods involve generating of a disturbance or perturbation on a
state of equilibrium over a short time range. The disturbance may be
temperature or pressure jump. The relaxation of the perturbated system is
monitored to a new state of equilibrium by spectrophotometric and fast
electronic devices. Radiofrequency and ultrasonic waves can also be used
to induce the disturbance and the relaxation can be monitored with
Nuclear Magnetic Resonance (NMR).

Techniques used for Monitoring Concentrations

For slow reactions, the composition of the reaction mixture can be
determined while the reaction is in progress either by withdrawing a small
sample or by monitoring the bulk. This is known as a real-time analysis.
Another option is to use the quenching method, in which reaction is
stopped at a certain time after initiation so that the composition may be
analysed at leisure. Quenching may be achieved in a number of ways such
as sudden cooling, adding a large amount of solvent, rapid neutralisation
of an acid reagent, removal of a catalyst or addition of a quencher. The
key requirement is that the reaction must be slow enough (or the
quenching method fast enough) for little reaction to occur during the
quenching process itself.

Often, the real time and quenching techniques are combined by

withdrawing and quenching small samples of the reaction mixture at
series of times during the reaction.

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CHM 423 COORDINATION CHEMISTRY

The composition of the reaction mixture may be followed in any one of a

variety of different ways by tracking any chemical or physical change that
occurs as the reaction proceeds. e.g.

 For reactions in which at least one reactant or product is a gas, the

reaction’s progress may be followed by monitoring the pressure,
or possibly the volume change.
 For reactions involving ions, conductivity or pH measurements
may often be employed.
 If the reaction is slow enough, the reaction mixture may be titrated.
 If one of the components is coloured, then colourimetry may be
appropriate.
 Absorption or emission spectroscopy are common (more on these
later)
 For reactions involving chiral compounds, polarimetry
(measurement of optical activity) may be useful.
 Other techniques include mass spectrometry, gas chromatography,
NMR/ESR, and many more.

3.4 Reaction Mechanism in Complexes

Reaction mechanism is a collection of elementary (one step) reactions that

would add up to result in the overall reaction. Generally, elementary
(simple) reactions are bimolecular and unimolecular, rarely are
termolecular. Experimentally determined rate law does not conform with
the stoichiometric coefficients of reactions, in general; unless the
mechanism itself is simple. Therein lies the need to propose a mechanism
for the reaction. A valid reaction mechanism must be consistent with the
experimental rate law. Reaction mechanism is the pathway leading to the
formation of the product or attainment of equilibrium in a given reaction.
There are two extreme cases in reaction mechanisms of complexes; SN1
(substitution Nucleophilic unimolecular reaction) and SN2 (substitution
Nucleophilic bimolecular reaction)

In SN1 mechanism, only one species occurs at the transition state. In such
a reaction, the departing ligand will leave before the attachment of the
incoming ligand, leading to a reduction in coordination number at the
transition state. An illustration is shown below, where X represents the
leaving group and Y the entering group.

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CHM 423 MODULE 4

The first stage is the rate determining step because it is slow. The
expression for the rate law can be written as R = k {[L5MX]n+} where k is
the rate constant and not equilibrium constant.

In SN2 mechanism, two species appear at the transition state. The

incoming ligand gets attached before the departure of the leaving group
leading to an increase in coordination number at the transition state. The
rate of the reaction is dependent on the concentrations of both the reacting
complex and the incoming ligand. The expression for rate law can be
presented as R = k {[L5MX]n+}[Y-]

Most often, complex reactions do not really fall into these two (SN1 and
SN2) extremes because the transition states in most cases are very difficult
to identify (or may not be detected). However, mechanisms of reactions
in complexes are between these extremes. When the contribution of the
incoming group to the transition state is small, the reaction mechanism
can be approximated to be SN1 but if the contribution is significant, the
reaction is approximated to SN2.

Further complication of the matter includes the fact that the rate law that
is determined for a reaction front kinetic data cannot be used to identify
the mechanisms for those reactions. This is so because the additional steps
in the overall substitution may take place, obscuring the simple first, a
second-order rate laws that are expected for molecular and bimolecular
processes respectively. The three most important cases that illustrate this
sort of complications are: (i) solvent intervention (ii) ion-pair formation
and (iii) conjugate-base formation. Thus, factors that influence the rate of
complex reactions are solvent intervention, ion-pair formation and
conjugate-base formation.

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CHM 423 COORDINATION CHEMISTRY

Solvent Intervention
Many reactions of complexes have been studied and examined in solvents
that are themselves ligands. Water, for example, is a respectable ligand,
and is present in the aqueous solution in high and effective constant
concentration. Since most reactions of complexes are studied in aqueous
system where water can act as ligand and abundant in extremely high
concentration, a possible reaction path is shown below

Where X and Y are neutral ligands

[L5MX] + H2O → [L5MOH2] + X slow
[L5MOH2] + Y → [L5MY] + H2O fast
Since the concentration of water is constant, the reaction can be
considered as SN1

Ion-Pair Formation
When the reacting complex and entering ligand are both ions, especially
when both have high charges, ion pair will form. It is also referred to as
outer-sphere complexes in some cases. In a reaction involving positively
charged complex and negatively charge ligand, the two reactants will be
attracted together by their electric charges. The greater the charges, the
greater the attractive force between the reactants. This will lead to
equilibrium.

[L5MX]n+ + Ym-⇌ {[L5MX]Y}n-m

K = [{[L5MX]Y}n-m]/ {[L5MX]n+}[Ym-]
{[L5MX]Y}n-m = K {[L5MX]n+}[Ym-]

If the reaction proceeds with speed by formation of the ion pair, the rate
of the reaction can be expressed as R= k K{[L5MX]n+}[Ym-] = k”
{[L5MX]n+}[Ym-], where k” as both kinetic and thermodynamic
contributions. This reaction can be considered as SN2 after further
investigation on the transition state composition.

Conjugate-Base Formation
When experimental rate laws contain [OH-], there is the question whether
[OH-] actually attacks the metal in a true associative fashion, or whether
it appears in the rate law through operation of mechanism. In this
conjugate base mechanism, the hydroxide first deprotonates a ligand for
instance NH3, forming the conjugate base here, leading to NH2–ligand. It
is then the conjugate base of the original metal complex that reacts with
the incoming ligand. There are two possibilities with a pH dependent
reaction, these possibilities are explained below;

 The rate law may include [OH-] such that the hydroxyl group
attacks the metal complex leading to SN2 reaction.
 The [OH-] may be involve in such a way that it reacts fast to

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CHM 423 MODULE 4

remove a proton from a protonated ligand in the reacting metal

complex forming a conjugate base (CB) which then reacts slowly
to substitute for the leaving group.

[Co(NH)5X]2+ + OH- → [Co(NH3)4(NH2)X]+ + H2O

[Co(NH3)4(NH2)X]+ + Y- → [Co(NH)5Y]2+

In the presence of a protonic hydrogen (ionisable), this proposed reaction

pathway is favourable and the rate law follow SN1 (CB), this implies that
the reaction is dependent on the concentration of the reacting complex in
the presence of OH-.

In the absence of a protonic hydrogen or if the removal of proton in the

above reaction is slow, the SN2 is most suitable reaction mechanism.
R = {[Co(NH3)5X]2+}[OH-]

SELF-ASSESSMENT EXERCISE

i. List three techniques used to study reaction kinetics

ii. Differentiate between kinetics and lability of complex
iii. With the aid of chemical equation and brief discussion, explain
chelate effect in metal complex reaction.

4.0 CONCLUSION

In conclusion, the thermodynamic stability studies of complexes provide

insight to the special stability of chelate complexes and their applications.
Stability of chelate is attributed to increase in entropy. Also, kinetics of
reactions shows the nature of reactions in complexes with different
mechanisms that are similar to, but not exactly, SN1 and SN2.

5.0 SUMMARY

In this unit, you have learnt that:

 Thermodynamic equilibrium of complexes has been studied and

the stability constants estimated.
 The ring formation and ring sizes effects on special stability of
chelate complexes have been studied and it has been established
that 5-membered ring chelates are very stable.
 Kinetic studies of complexes show that reactions of complexes are
only approximate to SN1 and SN2 and that the reactions
mechanisms are influenced by solvent, ion-pair formation and pH.

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CHM 423 COORDINATION CHEMISTRY

6.0 TUTOR-MARKED ASSIGNMENT

1. Identify the ligand that will give most stable complex with reason
2. Given that Cd2+ + 2en⇌[Cd(en)2]2+ has ΔH = 56.4KJ/mol and β =
1010.58 calculate the ΔG and ΔS for the reaction, gas constant, R, is
8.314J/Kmol. (Time allowed: 5 mins)
3. Comment on the results obtained in Activity 4.2 in relation to
chelate effect. (Time allowed: 3 mins)
4. Write the equations and stepwise formation constants for the
reaction in Activity 4.2 (Time allowed: 3 mins)
5. Explain the techniques used in kinetic studies briefly (Time
allowed: 6 mins)

7.0 REFERENCES/FURTHER READING

Cotton, F. A. & Wilkinson, G. (1972). Advanced Inorganic Chemistry

(3rd ed.). Inter-Science Publishers, A Division of John Wiley and
Sons.

Cox, P. A. (2004). Inorganic Chemistry (2nd ed.). BIOS Scientific

Publishers Taylor and Francis Group.

Figgis, B. N. & Hitchman, M. A. (2000). Ligand Field Theory and Its

Applications. New York: Wiley.

Gatech Edu. (2019). Stability of Coordination Compounds. Available at:

http://ww2.chemistry.gatech.edu/~barefield/1311/complexstabilit
y.pdf

Geoffrey, A. L. (2010). Introduction to Coordination Chemistry. John

Wiley and Sons, Ltd.

Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry (2nd ed.).

Pearson Education Limited.

Miessler, G. L. & Tarr, D. A. (2010). Inorganic Chemistry (3rd ed.).

Pearson Education Int.

Kettle, S. F. A. (1998). Physical Inorganic Chemistry: A Coordination

Approach. New York: Oxford University Press.

Porterfield, W. W. (1993). Inorganic Chemistry: A Unified Approach,

(2nd ed.).San Diego, CA.: Academic Press.

Singh, R. (2002). Coordination Chemistry: (1st ed.). Mittal Publication,

New Delhi, India, pp 121-123.

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

Organometallic Chemistry
*Organometallic chemistry:- The chemistry of compounds that contain

one or more metal–carbon bonds.

*Historical Background

*In (1760) Cadet of Paris military pharmacy, works on invisible inks

based on cobalt salt solutions. For their preparation, he uses cobalt

minerals that contain arsenic.

* The first olefin complex synthesized in (1827) by Zeise, who obtained

yellow needle-like crystals after refluxing a mixture of PtCl 4 and PtCl2 in

ethanol, followed by addition of KCl solution. Zeise’s salt was the first

compound identified as containing an organic molecule attached to a

metal using the pi electrons of the organic molecule. It is an ionic

compound of formula K[Pt(C2H4)Cl3].H2O [Potassium

trichloro(ethene)platinate(II)]; the structure of the anion, as shown

bellow; is based on a square plane, with three chloro ligands occupying

corners of the square and the ethylene occupying the fourth corner, but

perpendicular to the plane.

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

Anion of Zeise’s Salt

* 1852 Frankland prepares the important alkylmercury halides.

additionally: (C2H5)4Sn, (CH3)3B (1860). Frankland also introduced the

concept of valency (“combining power”) and the term “organometallic”.

*At (1852) C. J. Löwig and M. E. Schweizer in Zürich first prepare

(C2H5)4Pb from ethyl iodide and Na/Pb alloy. In a similar manner, they

also obtain (C2H5)3Sb and (C2H5)3Bi.

*In (1859) W. Hallwachs and A. Schafarik generate alkylaluminum

iodides

*In (1863) C. Friedel and J. M. Crafts prepare organochlorosilanes:

* The first organometallic compound containing the carbonyl ligand,

[PtCl2(CO)2] was discovered by P. Schützenberger in (1868).

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

* In (1890), Mond reported the preparation of the first binary metal

carbonyl compound, Ni(CO)4, a compound that became commercially

useful for the purification of nickel.

* Reactions between magnesium and alkyl halides, performed by Barbier

in (1898) and subsequently by Grignard led to the synthesis of alkyl

magnesium complexes now known as Grignard reagents, which used

extensively in organic synthesis.

*In (1909) W. J. Pope: prepared [(CH3)3PtI], the first σ-

organotransition-metal compound.

* In 1951, in an attempt to synthesize fulvalene from cyclopentadienyl

bromide, Kealy and Pauson reacted the Grignard reagent cyclo-

(C5H5)MgBr with FeCl3. This reaction did not yield fulvalene but an

orange solid having the formula (C5H5)2Fe, ferrocene. For each of the

cyclopentadienyl rings, all five of the C atoms are equidistant from the

metal ion, so that the two ring systems are parallel to each other just like

the slices of bread in a sandwich, with the metal stuck in between them.

The initial study indicated that the rings were in a staggered

conformation. Electron diffraction studies of gas-phase ferrocene, on the

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

other hand, showed the rings to be eclipsed, or very nearly so. More

recent X-ray diffraction studies of solid ferrocene have identified several

crystalline phases, with an eclipsed conformation at 98 K and with

conformations having the rings slightly twisted (Skew) in higher-

temperature crystalline modifications.

* Fischer’s group can also take credit for the discovery of the first metal–

carbon double bond, or carbene compound, [(CO)5W=C(OCH3)Ph], in

1964 and the first metal–carbon triple bond, or carbyne,

[(CO)4XCr≡CPh], in 1973.

*An other examples about sandwich compounds have been shown in the

following figure;

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

* The oldest organometallic compound known, vitamin B 12 coenzyme.

This naturally occurring cobalt complex contains a cobalt–carbon sigma

bond.

*Organic Ligands

Some common organic ligands are shown in Figure bellow. Special

nomenclature has been devised to designate the manner in which some of

these ligands bond to metal atoms; several of the ligands in Figure bellow

may bond through different numbers of atoms. The number of atoms

through which a ligand bonds is indicated by the Greek letter η (eta)

followed by a superscript indicating the number of ligand atoms attached

to the metal. For example, because the cyclopentadienyl ligands in

ferrocene bond through all five atoms, they are designated η5-C5H5. The

formula of ferrocene may therefore be written (η5-C5H5)2Fe. The η5-C5H5

ligand is designated the pentahaptocyclopentadienyl ligand. Hapto comes

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

from the Greek word for fasten; therefore, pentahapto means “fastened

in five places”.

* C5H5, probably the second ligand in organometallic chemistry (after

CO), most commonly bonds to metals through five positions, but under
certain circumstances, it may bond through only one or three positions.
As a ligand, C5H5 is commonly abbreviated Cp. The corresponding
formulas and names are designated as follows;

*The table below represents the most commone ligand in organometalic

chemistry:-

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

* For ligands having all carbons bonded to a metal, sometimes the

superscript is omitted. Ferrocene may therefore be written (η-C5H5)2Fe

and dibenzenechromium (η-C6H6)2Cr. Similarly, π with no superscript

may occasionally be used to designate that all atoms in the pi system are

bonded to the metal; (for example, (π-C5H5)2Fe).

*Hapticity

* The hapticity of the ligand, defined as the number of C atoms in the

ligand that are directly bonded to the metal.

The 18-Electron Rule

In main group chemistry, we have encountered the octet rule, in which

electronic structures can be rationalized on the basis of a valence shell

requirement of 8 electrons. Similarly, in organometallic chemistry, the

electronic structures of many compounds are based on a total valence

electron count of 18 on the central metal atom. As with the oct et rule,

there are many exceptions to the 18-electron rule, but the rule

nevertheless provides useful guidelines to the chemistry of many

organometallic complexes, especially those containing strong π -acceptor

ligands.

*Because the transition metals can use their valence d-orbitals in their

bonding, many (but not all) organometallic compounds follow the

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

Effective Atomic Number (EAN) rule of Sidgwick, otherwise known as

the 18-electron rule.

*Just as some main group compounds violate the “octet rule” (for

example, BCl3 is electron-deficient while SF6 is hypervalent),

*Changes in the number of valence electrons has a profound influence on

the bonding, structure, and reactions of a compounds.

*low oxidation state organometallic complexes tend to obey the 18 -

electron rule via bonding with π-acceptor ligands.

* This 18-electron rule often breaks down for early and late d-block

metals. The majority of organometallic compounds with metals from the

middle of the d-block obey the 18-electron rule.

*16-electron complexes are common for e.g. Rh(I), Ir(I), Pd(0) and Pt(0).

*Counting Electrons:-

*The group number represents the number of valence electron as shown

in table below:-

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*The table below represents Electron Counting Schemes for Common

Ligands:-

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*There are two models of electron counting; Covalent and ionic models.

Compound Covalent Model Ionic Model

MoH4(PR3)4

Mo(C6H6)2

(η5-C5H5)Fe(CO)2 Cl

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*According to 18-electron Rule The central transition metal can

accommodate electrons in the s, p, and d orbitals. s (2) , p (6) , and d (10)

= maximum of 18 es.

*Many stable organometallic compounds have an electron count other

than 18; otherwise, most non-18e structures have <18e, such as [MeTiCl3,

(8e); [Me2NbCl3, (10e)]; [WMe6, (12e)]; [Pt(PCy3)2, (14e)]; [M(H2O)6]2+

(M = V, 15e; Cr, 16e; Mn, 17e; Fe, 18e)]. Much rarer are d block

examples with >18e: CoCp2, 19e; and NiCp2, 20e are prominent cases.

Exceptions to the 18 electron rule

*Square planar organometallic complexes of the late transition metals

(16e).

• Some organometallic complexes of the early transition metals (e.g.

Cp2TiCl2, WMe6, Me2NbCl3, CpWOCl3) [ A possible reason for the same

is that some of the orbitals of these complexes are too high in energy for

effective utilization in bonding or the ligands are mostly σ donors.

* Some high valent d0 complexes have a lower electron count than 18.

* Sterically demanding bulky ligands force complexes to have less than

18 electrons.

* The 18 electron rule fails when bonding of organometallic clusters of

moderate to big sizes (6 Metal atoms and above) are considered.

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* The rule is not applicable to organometallic compounds of main

group metals as well as to those of lanthanide and actinide metals.

**There are quite a few examples of organometallics which have 16 VE.

As with all chemistry, the excuse is either electronic or steric (or both).

(i) Electronic effects

Late transition metals with d8 electron configurations e.g. Rh(I), Ir(I),

Pd(II), Pt(II) have a strong tendency to form square planar 16 VE

complexes. Similarly, d10 complexes tend to form trigonal 16 VE

complexes. As the atomic number Z increases, the d-shell is stabilized

(lowers in energy). The occupied dz2 orbital (perpendicular to the plane)

is no longer involved in ligand bonding.

(ii) Steric Effects

Early transition metals have fewer d-electrons to start with than the

middle and late transition metals, so they must achieve their 18e count by

coordination of a larger number of ligands. If the ligands involved are too

bulky, then low-electron count complexes are formed.

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* Steric effects can produce low-coordinate (not many ligands)

complexes which often have <18 electrons.

* For early transition metals (e.g. with d0 metals) it is often not possible

to fit the number of ligands necessary to reach 18 electrons around the

metal.

** Linear complexes (d10, 14 electrons)

*d10-metals with 2 ligands, so 14-electron complexes.

*Common for Ag(I), Au(I) and Hg(II), Less common for Cu(I), Zn(II)

and Cd(II).

Explanation:

* For d10 compounds, there is a relatively small energy difference

between the d, s and p orbitals (e.g. 5d, 6s and 6p for Au(I)).

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* This permits extensive hybridization between the dz 2, s and pz orbitals

as shown below:

* More common for group 11 (Cu, Ag, Au) than group 12 (Zn, Cd, Hg)

because the energy difference between the d, s and p-orbitals is smaller

for group 11.

* More common for the heavier elements (Ag(I), Au(I), Hg(II). However,

there are also lots of tetrahedral complexes of Ag(I), Au(I), Cu(I), Zn(II),

Cd(II) and Hg(II) (e.g. 14 e- linear [(R3P)AuCl] + 2 PR3 == 18 e-

tetrahedral [(R3P)3AuCl]).
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**Strong oxidants or reductants

* Many 18 electron compounds can be reduced or oxidised to give 17 or

19 electron compounds, respectively. Such compounds are often good

oxidizing or reducing agents (i.e. they want to get back to being 18 -

electron compounds).

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*Why 18 Electrons?

A good example of a complex that obey to the 18-electron rule is

Cr(CO)6. The molecular orbitals of interest in this molecule are those that

result primarily from interactions between the d orbitals of Cr and the σ-

donor (HOMO) and π-acceptor orbitals (LUMO) of the six CO ligands.

The relative energies of molecular orbitals resulting from these

interactions are shown in below.

Chromium(0) has 6 electrons outside its noble gas core. Each CO

contributes a pair of electrons to give a total electron count of 18es.. In

the molecular orbital diagram, these 18 electrons appear as the (12 σ)

electrons—the σ electrons of the CO ligands, stabilized by their

interaction with the metal orbitals—and the (6 t2g) electrons. Addition of

one or more electrons to Cr(CO)6 would populate the eg orbitals, which

are antibonding; the consequence would be destabilization of the

molecule. Removal of electrons from Cr(CO)6 would depopulate the t2g

orbitals, which are bonding as a consequence of the strong π-acceptor

ability of the CO ligands; a decrease in electron density in these orbitals

would also tend to destabilize the complex. The result is that the 18

electron configuration for this molecule is the most stable.

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*Exercise :- Assuming the eighteen electron rule is obeyed, what are the

values of t-z and the oxidation state of the metal in (a)-(g)?

(a) [Mn(CO)t(Me)]

(b) [Fe Cp (CO)n]+1 Cl-1

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(C) [CoH(CO)v]

(d) [Os(H)w(PPh3)]

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(h) where M= one of second raw metal

(i)

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*The 18-electron rule assist us to predict the structure of organometallic

compound, Look at CO complexes of Mn. You may expect to have the

following structure for a CO complex of Mn.

CO
OC Mn CO
OC CO
But in fact the structure as follows;

**Ligands in Organometallic Chemistry:-

Hundreds of ligands are known to bond to metal atoms through carbon.

Carbon monoxide forms a very large number of metal complexes and

deserves special mention, along with several similar diatomic ligands.

Many organic molecules containing linear or cyclic pi systems also form

numerous organometallic complexes. Special attention will be paid to two

types of organometallic compounds that are especially important: carbene

complexes, containing metal–carbon double bonds, and carbyne

complexes, containing metal–carbon triple bonds.

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* Carbonyl (CO) Complexes

Carbon monoxide is the most common ligand in organometallic

chemistry. It serves as the only ligand in binary carbonyls such as

Ni(CO)4, W(CO)6, and Fe2(CO)9 or, more commonly, in combination

with other ligands, both organic and inorganic. CO may bond to

a single metal, or it may serve as a bridge between two or more metals.

We will consider the bonding between metals and CO, the synthesis and

reactions of CO complexes, and examples of various types of CO

complexes.

*Table below lists many of the stable, neutral, d-block metal

carbonyl compounds;

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*Bonding of CO ligand

It is useful to review the bonding in CO. The molecular orbital picture of

CO shown in Figure below;

*The molecular orbitals derived primarily from the 2p atomic orbitals of

these molecules are shown in Figure below;

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The highest energy occupied molecular orbital (HOMO) has its largest

lobe on carbon. It is through this orbital, occupied by an electron pair,

that CO exerts its σ-donor function, donating electron density directly

toward an appropriate metal orbital, such as an unfilled d or hybrid

orbital. Carbon monoxide also has two empty p* orbitals (the lowest

energy unoccupied molecular orbital , (LUMO); these also have larger

lobes on carbon than on oxygen. A metal atom having electrons in a d

orbital of suitable symmetry can donate electron density to these p*

orbitals. These σ-donor and π-acceptor interactions are illustrated in

Figure below;

*The -donor interaction increases the electron density on the metal and

decreases the electron density on the CO ligand. The -acceptor

interaction decreases the electron density on the metal and increases the

electron density on the CO ligand. Both effects ‘reinforce’ each other.

Sometimes referred to as (synergic bonding).

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* The strength of this bonding depends on several factors, including

the charge on the complex and the ligand environment of the metal.

* If this picture of bonding between CO and metal atoms is correct, it

should be supported by experimental evidence. Two sources of such

evidence are infrared spectroscopy and X-ray crystallography. First, any

change in the bonding between carbon and oxygen should be reflected in

the C-O stretching vibration as observed by IR. The C-O stretch in

organometallic complexes is often very intense (stretching the C-O bond

results in a substantial change in dipole moment), and its energy often

provides valuable information about the molecular structure. Free

–1
carbon monoxide has a C-O stretch at (2143 cm ). Cr(CO)6, on the

other hand, has its C-O stretch at (2000 cm – 1). The lower energy for the

stretching mode means that the C-O bond is weaker in Cr(CO)6.

* Both σ donation and π acceptance would be expected to weaken the C-

O bond and to decrease the energy necessary to stretch that bond.

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*Additional evidence is provided by X-ray crystallography. In carbon

monoxide, the C-O distance has been measured at 112.8 pm. Weakening

of the C-O bond would be expected to cause this distance to increase.

Such an increase in bond length is found in complexes containing CO,

with C-O distances approximately 115 pm for many carbonyls.

* The charge on a carbonyl complex is also reflected in its infrared

spectrum. Five isoelectronic hexacarbonyls have the following C-O

stretching bands (compare with n(CO) = 2143 cm- 1 for free CO):

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Note:- The positions of the C-O stretching vibrations in previous ions

may be affected by interactions with solvents or counter ions, and solid

and solution spectra may differ slightly.

* Of these isoelectronic five ions, [Ti(CO)6]2- contains the most highly

reduced metal, formally containing Ti(2-); this means that titanium has

the weakest ability to attract electrons and the greatest tendency to back-

donate electron density to CO. The formal charges on the metals increase

from (-2) for [Ti(CO)6]2- to (+2) for [Fe(CO)6]2+. The titanium in

[Ti(CO)6]2-, with the most negative formal charge, has the strongest

tendency to donate to CO. The consequence is strong population of the π*

orbitals of CO in [Ti(CO)6]2- and reduction of the strength of the C-O

bond. In general, the more negative the charge on the organometallic

species, the greater the tendency of the metal to donate electrons to the

π* orbitals of CO, and the lower the energy of the C-O stretching

vibrations.
2+
* How is it possible for cationic carbonyl complexes such as [Fe(CO) 6]

to have C-O stretching bands even higher in energy than those in free

CO? It seems clear that the CO ligand does not engage in significant π-

acceptor activity in these complexes, so weakening of the C-O bond via

this interaction should be minimal, but how does the strength of the bond

increase? Calculations have demonstrated that a polarization effect

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caused by the metal cation plays a major role in these carbonyl cations. In

free CO, the electrons are polarized toward the more electronegative

oxygen. For example, the electrons in the p orbitals are concentrated

nearer to the oxygen atom than to the carbon. The presence of a transition

metal cation reduces the polarization in the C-O bond by attracting the

bonding electrons:

The consequence is that the electrons in the positively charged complex

are more equally shared by the carbon and the oxygen, giving rise to a

stronger bond and a higher-energy C-O stretch.

* The very high ν(CO) bands result from weak back donation. When the

frequency of carbonyls appears at higher energy band of free CO, the

complexes are sometimes called nonclassical carbonyls.

-
* Exercise:- Predict which of the complexes [V(CO)6] , Cr(CO)6, or

+
[Mn(CO)6] has the shortest C-O bond.

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** Bridging Modes of CO
* Many cases are known in which CO forms bridges between two or

more metals. Many bridging modes are known Table below.

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*The bridging mode is strongly correlated with the position of the C-O

stretching band. In cases in which CO bridges two metal atoms, both

metals can contribute electron density into π* orbitals of CO to weaken

the C-O bond and lower the energy of the stretch. Consequently, the C-O

stretch for doubly bridging CO is at a much lower energy than for

terminal COs. An example is shown in Figure above.

* Interaction of three metal atoms with a triply bridging (as shown in

figure below) CO further weakens the C-O bond; the infrared band for

the C-O stretch is still lower than in the doubly bridging case.

* Ordinarily, terminal and bridging carbonyl ligands can be considered 2

electron donors, with the donated electrons shared by the metal atoms in

the bridging cases. For example, in the complex below, the bridging CO

is a 2-electron donor overall, with a single electron donated to each

metal. The electron count for each Re atom according to covalent method

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**There are three points of interest with respect to metal carbonyls:-

1) CO is not ordinarily considered a very strong Lewis base, and yet

it forms strong bonds to the metals in these compounds.

2) The metals are always in a low oxidation state, most often formally

in an oxidation state of Zero, but also in low positive & negative

oxidation states.

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3) The 18-electrons rule is obeyed with remarkable frequency,

perhaps 99% of the time.

**Metals with odd atomic number cant satisfy the 18-es. By simple

addition of CO ligand, since the resultant moiety will have an odd

number of electrons. In such case there are several option open to

these metals by which the 18-es. Rule can be satisfied:-

A. The addition of an electron by reducing agent to form an anion

such as [V(CO)6]-.

B. The electron deficient moiety can bond covalently with an

atom or group that also has single unpaired electron available,

example:- hydrogen or chlorine : HM(CO)n or M(CO)nCl .

C. If no either species are available with which to react, two

moieties each with an odd atom can dimerized with resultant

pairing of the odd electrons, examples

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* Binary Carbonyl Complexes

Binary carbonyls, containing only metal atoms and CO, are numerous.

Most of these complexes obey the 18-electron rule. The cluster

compounds Co6(CO)16 and Rh6(CO)16 do not obey the rule.

* One other binary carbonyl does not obey the rule, the 17 -electron

V(CO)6. This complex is one of a few cases in which strong π-acceptor

ligands do not afford an 18-electron configuration. In V(CO)6, the

vanadium is apparently too small to permit a seventh coordination

site; hence, no metal–metal bonded dimer, which would give an 18

electron configuration, is possible. However, V(CO)6 is easily reduced to

-
[V(CO)6] , an 18-electron complex.

* An interesting feature of the structures of binary carbonyl complexes is

that the tendency of CO to bridge transition metals decreases going down

the periodic table. For example, in Fe2(CO)9 there are three bridging

carbonyls; but in Ru2(CO)9 and Os2(CO)9, there is a single bridging CO.

A possible explanation is that the orbitals of bridging CO are less able to

interact effectively with transition-metal atoms as the size of the metals

increases, along with the metal–metal bond lengths.

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* Exercise:- Verify the 18-electron rule for five of the binary carbonyls—

other than V(CO)6, Co6(CO)16, and Rh6(CO)16i shown in Figure below.

*Figure below represents some of binary carbonyl complexes:-

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**Synthesis of Binary Carbonyl Complexes

Binary carbonyl complexes can be synthesized in many ways. Several of
the most common methods are as follows:
1) Direct reaction of a transition metal with CO. The most
facile of these reactions involves nickel, which reacts with CO at
ambient temperature and 1 atm:

Ni(CO)4 is a volatile, extremely toxic liquid that must be handled

with great caution. Because the reaction can be reversed at high
temperature, coupling of the forward and reverse reactions has
been used commercially in the Mond process for obtaining purified
nickel from ores. Other binary carbonyls can be obtained from
direct reaction of metal powders with CO, but elevated
temperatures and pressures are needed. For example

2) Reductive carbonylation: reduction of a metal compound in the

presence of CO and an appropriate reducing agent. Examples are
shown below.

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*Some of metal carbonyls prepared from reducing their oxides at 300 C 0

and 300 atm.

3) Thermal or photochemical reaction of other binary

carbonyls. Examples are

*The most common reaction of carbonyl complexes is CO dissociation.

This reaction, which may be initiated thermally or by absorption of
ultraviolet light, characteristically involves loss of CO from an 18-
electron complex to give a 16-electron intermediate, which
may react in a variety of ways, depending on the nature of the complex
and its environment. A common reaction is replacement of the lost CO by
another ligand to form a new 18-electron species as product. For
example,

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*This type of reaction therefore provides a pathway in which CO

complexes can be used as precursors for a variety of complexes of other
ligands.
**Oxygen-Bonded Carbonyls
One additional aspect of CO as a ligand deserves mention: it can
sometimes bond through oxygen as well as carbon. This phenomenon
was first noted in the ability of the oxygen of a metal–carbonyl complex
to act as a donor toward Lewis acids such as AlCl 3, with the overall
function of CO serving as a bridge between the two metals.
Many examples are known in which CO bonds through its oxygen
to transition metal atoms, with the C-O-metal arrangement generally
bent. Attachment of a Lewis acid to the oxygen results in significant
weakening and lengthening of the C-O bond and a shift of the C-O
stretching vibration to lower energy in the infrared. This shift is typically
between 100 and 200 cm -1. Examples of O-bonded carbonyls, sometimes
called isocarbonyls, are in Figure below.

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**Ligands Similar to CO
*CS (thiocarbonyl), CSe (selenocarbonyl), and CTe (tellurocarbonyl), are
similar to CO in their bonding modes in that they behave as both σ-
donors and π-acceptors and can bond to metals in terminal or bridging
modes.
* In several cases, isostructural complexes of the ligands CO through CTe
have been prepared, providing opportunities for structural and
spectroscopic comparisons. Data from a set of ruthenium complexes are
provided in table below;

* The decrease in ruthenium—carbon distance in going down this series

is consistent with increasing π-acceptor activity of the ligands, populating
orbitals that are bonding with respect to the Ru—C bond. Although
increasing π-acceptor ability of the ligands accounts for some of the
decrease in C—E stretching frequency.

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*Other ligands are isoelectronic with CO and, not surprisingly, exhibit

structural and chemical parallels with CO. Two examples are CN- and N2.
Complexes of CN- have been known longer than carbonyl complexes.
Blue complexes (Prussian blue and Turnbull’s blue) containing the ion
[Fe(CN)6]3- have been used as pigments in paints and inks for
approximately three centuries. Cyanide is a stronger σ-donor and a
substantially weaker π-acceptor than CO; overall, it is close to CO in the
spectrochemical series.
* The discovery that hydrogenase enzymes contain both CO and CN-
bound to iron has stimulated interest in complexes containing both
ligands. Remarkably, only two iron complexes containing both CO and
CN- and a single iron atom, [Fe(CO)(CN)5]3- (reported in 1887) and
[Fe(CO)4(CN)]- (reported in 1974), were known before 2001. Both the
cis and trans isomers of [Fe(CO)2(CN)4]2- and fac-[Fe(CO)3(CN)3]- have
been prepared. Two of the mixed ligand complexes can be made using
Fe(CO)4I2 .

The complex trans-[Fe(CO)2(CN)4]2- can be made by the addition of

cyanide to a solution of FeCl2 under an atmosphere of CO:

* Dinitrogen is a weaker donor and acceptor than CO.

** NO Complexes
The NO (nitrosyl) ligand shares many similarities with CO. Like CO, it is
a σ-donor and π-acceptor and can serve as a terminal or bridging ligand;
useful information can be obtained about its compounds by analysis of its

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infrared spectra. Unlike CO, however, terminal NO has two common

coordination modes, linear (like CO) and bent. Examples of NO
complexes are in figure below.

* NO+ is isoelectronic with CO; therefore, in its bonding to metals, linear

NO is considered by electron counting scheme (ionic model) as NO+, a
2-electron donor. By the (covalent model), linear NO is counted as a 3-
electron donor (it has one more electron than the 2-electron donor CO).
* The bent coordination mode of NO can be considered to arise formally
from NO-, with the bent geometry suggesting sp2 hybridization at the
nitrogen. By electron-counting scheme (ionic model), therefore, bent NO
is considered the 2-electron donor NO-, by the (covalent model), it is
considered a 1-electron donor.
* Useful information about the linear and bent bonding modes of NO is
summarized in Figure below. Many complexes containing each mode are
known, and examples are also known in which both linear and bent NO
occur in the same complex. Although linear coordination usually gives
rise to N-O stretching vibrations at a higher energy than the bent mode,
there is enough overlap in the ranges of these bands that infrared spectra
alone may not be sufficient to distinguish between the two. Furthermore,
the manner of packing in crystals may bend the M-N-O bond
considerably from 180° in the linear coordination mode.

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* One compound containing only NO ligands is known, Cr(NO)4, a

tetrahedral molecule that is isoelectronic with Ni(CO)4. Complexes
containing bridging nitrosyl ligands are also known, with the neutral
bridging ligand formally considered a 3 -electron donor. One NO
complex, the nitroprusside ion, [Fe(CN)5(NO)]2-, has been used as a
vasodilator in the treatment of high blood pressure. Its therapeutic effect
is a consequence of its ability to release its NO ligand; the NO acts as the
vasodilating agent.

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* NS (thionitrosyl). Like NO, NS can function in linear, bent, and

bridging modes. In general, NS has been reported to act as a stronger σ-
donor but weaker π-acceptor ligand than NO, a consequence of the
greater concentration of negative charge on the nitrogen atom in NS. The
difference in polarity of the NO and NS ligands also leads to significant
differences in the electronic spectra of their complexes. The realm of NSe
(selenonitrosyl) complex chemistry is limited; only a single complex of
this ligand has been reported.

** Hydride and Dihydrogen Complexes

* Hydride Complexes
Although hydrogen atoms form bonds with nearly every element, we will
specifically consider coordination compounds containing H bonded to
transition metals. Because the hydrogen atom only has a 1s orbital of
suitable energy for bonding, the bond between H and a transition metal
must be a σ-interaction, involving metal s, p, and/or d orbitals. As a
ligand, H may be considered a 2-electron donor as hydride (H-, ionic
model) or a 1-electron neutral donor (H atom, covalent model).
Although some transition-metal complexes containing only the hydride
ligand are known—an example is the 9-coordinate [ReH9]2- ion ( Figure
below), the classic example of a tricapped trigonal prism.

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* Compounds containing only a single ligand, such as NO in Cr(NO)4

and CO in Mo(CO)6, are called homoleptic compounds.
* We are principally concerned with complexes containing H in
combination with other ligands. Such complexes may be made in a
variety of ways. Probably the most common synthesis is by reaction of a
transition metal complex with H2. For example,

Carbonyl hydride complexes can also be formed by the reduction of

carbonyl complexes, followed by the addition of acid. For example,

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* Dihydrogen Complexes
The first structural characterization of a dihydrogen complex did not
occur until 1984, when Kubas synthesized M(CO)3(PR3)2(H2), where M
= Mo or W and R = cyclohexyl or isopropyl. Subsequently, many H 2
complexes have been identified, and the chemistry of this ligand has
developed rapidly.
* The bonding between dihydrogen and a transition metal can be
described as shown in Figure below. The σ-electrons in H2 can be
donated to a suitable empty orbital on the metal (such as a d orbital or
hybrid orbital), and the empty σ* orbital of the ligand can accept electron
density from an occupied d orbital of the metal. The result is an overall
weakening and lengthening of the H-H bond in comparison with free
H2. Typical H-H distances in complexes containing coordinated
dihydrogen are in the range of 82 to 90 pm, in comparison with 74.14 pm
in free H2.

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* If the metal is electron rich and donates strongly to the σ* of H2 the H-

H bond in the ligand can rupture, giving separate H atoms.
Consequently, the search for stable H2 complexes has centered on metals
likely to be relatively poor donors, such as those in high oxidation states
or surrounded by ligands that function as strong electron acceptors. In
particular, good π-acceptors, such as CO and NO, can be effective at
stabilizing the dihydrogen ligand.
* E X E R C I S E: Explain why Mo(PMe3)5H2 is a di-hydride (contains
two separate H ligands), but Mo(CO)3(PR3)2(H2) contains the
dihydrogen ligand (Me = methyl, R = isopropyl).
Ans. PMe3 is a stronger σ-donor and weaker π-acceptor than CO.
Therefore, the Mo in Mo(PMe3)5H2 has a greater concentration of
electrons and a greater tendency to back-bond to the hydrogens by
donating to the σ* orbital of H2. This donation is strong enough to
rupture the H-H bond, converting H2 into two hydride ligands.

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**Ligands Having Extended π-Systems

*Linear π-Systems

The simplest case of an organic molecule having a linear π-system is

ethylene, which has a single π-bond resulting from the interactions of two

2p orbitals on its carbon atoms. Interactions of these p orbitals result in

one bonding and one antibonding π-orbital, as shown:

*The antibonding interaction has a nodal plane perpendicular to the

internuclear axis, but the bonding interaction has no such nodal plane.

*Next is the three-atom π-system, the π-allyl radical, C3H5. In this case,

there are three 2p orbitals to be considered, one from each of the carbon

atoms participating in the π-system. The possible interactions are as

follows:

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*The lowest energy π-molecular orbital for this system has all three p

orbitals interacting constructively, to give a bonding molecular orbital.

Higher in energy is the nonbonding orbital (πn), in which a nodal plane

bisects the molecule, cutting through the central carbon atom.

*In this case, the p orbital on the central carbon does not participate in the

molecular orbital; a nodal plane passes through the center of this π-orbital

and thereby cancels it from participation. Highest in energy is the

antibonding π* orbital, in which there is an antibonding interaction

between each neighboring pair of carbon p orbitals.

*The number of nodes perpendicular to the carbon chain increases in

going from lower energy to higher energy orbitals; for example, in the π-

allyl system, the number of nodes increases from zero to one to two from

the lowest to the highest energy orbital. This is a trend that will also

appear in the following examples.

*The term “linear” is used broadly to include not only ligands that have

carbons in a straight line but acyclic ligands that are bent at inner sp2

carbons.

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**Bonding between Metal Atoms and Organic Pi Systems

*Linear Pi Systems

*π–Ethylene Complexes

Many complexes involve ethylene, C2H4, as a ligand, including the anion

of Zeise’s salt, [Pt(η2-C2H4)Cl3]-. In such complexes, ethylene

commonly acts as a sidebound ligand with the following geometry with

respect to the metal:

*The hydrogens in ethylene complexes are bent back away from the

metal, as shown. Ethylene donates electron density to the metal in a

sigma fashion, using its π-bonding electron pair, as shown in Figure

below. At the same time, electron density can be donated back to the

ligand in a pi fashion from a metal d orbital to the empty π* orbital of the

ligand. This is another example of the synergistic effect of s donation and

π-acceptance.

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*The C-C distance in Zeise’s salt is 137.5 pm in comparison with 133.7

pm in free ethylene. The lengthening of this bond can be explained by

a combination of the two factors involved in the synergistic σ-donor, π-

acceptor nature of the ligand: donation of electron density to the metal in

a sigma fashion reduces the π-bonding electron density within the ligand,

weakening the C-C bond. The net effect weakens and lengthens the C-C

bond in the C2H4 ligand.

*In addition, vibrational frequencies of coordinated ethylene are at lower

energy than in free ethylene; for example, the C=C stretch in the anion of

Zeise’s salt is at 1516 cm-1, compared to 1623 cm–1 in free ethylene.

*π–Allyl Complexes

*The allyl group most commonly functions as a trihapto ligand, using

delocalized π-orbitals as described previously, or as a monohapto ligand,

primarily σ-bonded to a metal. Examples of these types of coordination

are in Figure below.

*The lowest energy π-orbital can donate electron density in a sigma

fashion to a suitable orbital on the metal. The next orbital, nonbonding in

free allyl, can act as a donor or acceptor, depending on the electron

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distribution between the metal and the ligand. The highest energy π-

orbital acts as an acceptor; thus, there can be synergistic sigma and pi

interactions between allyl and the metal. The C-C-C angle within the

ligand is generally near 120°, consistent with sp2 hybridization.

*Allyl complexes (or complexes of substituted allyls) are intermediates in

many reactions, some of which take advantage of the capability of this

ligand to function in both a η3 and η1 fashion. Loss of CO from carbonyl

complexes containing η1-allyl ligands often results in conversion of η1-

allyl to η3-allyl. For example,

The [Mn(CO)5]- ion displaces Cl- from allyl chloride to give an 18-

electron product containing η1-C3H5. The allyl ligand switches to trihapto

when a CO is lost, preserving the 18-electron count.

*Other Linear Pi Systems

Many other such systems are known; several examples of organic ligands

having longer π-systems are in Figure below. Butadiene and longer

conjugated π-systems have the possibility of isomeric ligand forms (cis

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and trans for butadiene). Larger cyclic ligands may have a π-system

extending through part of the ring. An example is cyclooctadiene

(COD); the 1,3-isomer has a 4-atom π-system comparable to butadiene;

1,5-cyclooctadiene has two isolated double bonds, one or both of which

may interact with a metal in a manner similar to ethylene.

*Exercise:Identify the transition metal in the following 18 -electron

complexes: a.(η5-C5H5)(cis-η4C4H6)M(PMe3)2(H) (M)=second row

transition metal) b. (η5-C5H5)M(C2H4)2 (M = frst-row transition metal).

**Cyclic π-Systems

*Cyclopentadienyl (Cp) Complexes

The cyclopentadienyl group, C5H5, may bond to metals in a variety of

ways, with many examples known of the η1-, η3-, and η5-bonding modes.

The discovery of the first cyclopentadienyl complex, ferrocene, was a

landmark in the development of organometallic chemistry and stimulated

the search for other compounds containing π-bonded organic

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ligands. Substituted cyclopentadienyl ligands are also known, such as

C5(CH3)5, often abbreviated Cp*, and C5(benzyl)5.

* Ferrocene and other cyclopentadienyl complexes can be prepared by

reacting metal salts with NaC5H5.

* Ferrocene, (η5-C5H5)2Fe

Ferrocene is the prototype of a series of sandwich compounds, the

metallocenes, with the formula (C5H5)2M. Electron counting in ferrocene

can be viewed in two ways. One possibility is to consider it an iron(II)

complex with two 6-electron cyclopentadienide (C5H5-) ions, another to

view it as iron(0) coordinated by two neutral, 5 -electron C5H5 ligands.

The actual bonding situation in ferrocene is more complicated and

requires an analysis of the various metal–ligand interactions.

*As usual, we expect orbitals on the central Fe and on

the two C5H5 rings to interact if they have appropriate symmetry;

furthermore, we expect interactions to be strongest if they are between

orbitals of similar energy.

* Other Metallocenes and Related Complexes

Other metallocenes have similar structures but do not necessarily obey

the rule. For example, cobaltocene and nickelocene are structurally

similar 19- and 20-electron species.

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* The extra electrons have chemical and physical consequences, as can be

seen from comparative data in Table above.

* Electrons 19 and 20 of the metallocenes occupy slightly antibonding

orbitals; as a consequence, the metal–ligand distance increases, and ΔH

for metal–ligand dissociation decreases. Ferrocene shows much more

chemical stability than cobaltocene and nickelocene; many of the

chemical reactions of the latter are characterized by a tendency to yield

18-electron products. For example, ferrocene is unreactive toward iodine

and rarely participates in reactions in which other ligands substitute for

the cyclopentadienyl ligand. However, cobaltocene and nickelocene

undergo reactions to give 18-electron products:

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* Cobalticinium reacts with hydride to give a neutral, 18 -electron

sandwich compound in which one cyclopentadienyl ligand has been

modified into η4-C5H6 (Figure below)

Ferrocene,. It undergoes a variety of reactions, including many on the

cyclopentadienyl rings. A good example is that of electrophilic

acyl substitution (Figure below), a reaction paralleling that of benzene

and its derivatives. In general, electrophilic aromatic substitution

reactions are much more rapid for ferrocene than for benzene, an

indication of greater concentration of electron density in the rings of the

sandwich compound.

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*Binuclear metallocenes with two atoms, rather than one in the center of
a sandwich structure are also known. Perhaps the best known of these
metallocenes is decamethyldizincocene, (η5-C5Me5)2Zn2 (Figure
below), which was prepared from decamethylzincocene, (η5-C5Me5)2Zn,
and diethylzinc. Particularly notable is (η5-C5Me5)2Zn2, the first example
of a stable molecule with a zinc–zinc bond; moreover, its zinc atoms are
in the exceptionally rare +1 oxidation state.

*A variation on the theme of metallocenes and related sandwich

compounds is provided by the “inverse” sandwich in Figure below, with
calcium(I) ions on the outside and the cyclic pi ligand 1,3,5-
triphenylbenzene in between. This compound was most efficiently
prepared by reacting 1,3,5-triphenylbenzene with activated calcium in
THF solvent using catalytic amounts of 1-bromo-2,4,6 triphenylbenzene.
Although the product of this reaction is highly sensitive to moisture and
air and it represents a rare example of a +1 oxidation state among the
alkaline earths.

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**Complexes Containing Cyclopentadienyl and CO Ligands

Many complexes are known containing both Cp and CO ligands. These

include “half-sandwich” compounds such as (η5-C5H5)Mn(CO)3 and

dimeric and larger cluster molecules. Examples are in Figure below. As

for the binary CO complexes, complexes of the second- and third-row

transition metals show a decreasing tendency of CO to act as a

bridging ligand.

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*Many other linear and cyclic pi ligands are known. Examples of

complexes containing some of these ligands are in Figure below.

Depending on the ligand and the electron requirements of the metal (or

metals), these ligands may be capable of bonding in a mono-hapto or

polyhapto fashion, and they may bridge two or more metals.

**

Complexes containing direct metal–carbon single, double, and triple

bonds have been studied extensively. Table below gives examples of the
most important types of ligands in these complexes.

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*Alkyl and Related Complexes

Some of the earliest known organometallic complexes were those having

σ-bonds between main group metal atoms and alkyl groups. Examples

include Grignard reagents, having magnesium–alkyl bonds, and alkyl

complexes with alkali metals, such as methyllithium. Stable transition

metal alkyls were initially synthesized in the first decade of the twentieth

century; many such complexes are now known. The metal–ligand

bonding in these complexes may be viewed as primarily involving

covalent sharing of electrons between the metal and the carbon in a sigma

fashion:

In terms of electron counting, the alkyl ligand may be considered a 2-

electron donor :CR3- (Ionic model) or a 1-electron donor .CR3 (covalent

model). Significant ionic contribution to the bonding may occur in

complexes of highly electropositive elements, such as the alkali metals

and alkaline earths.

*Many synthetic routes to transition-metal alkyl complexes have been

developed. Two of the most important of these methods are:

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1- Reaction of a transition-metal halide with organolithium,

organomagnesium, or organoaluminum reagent

2- Reaction of a metal carbonyl anion with an alkyl halide

Although many complexes contain alkyl ligands, transition-metal

complexes that contain alkyl groups as the only ligands, are relatively

rare. Examples include Ti(CH3)4, W(CH3)6, and Cr[CH2Si(CH3)3]4.

Alkyl complexes have a tendency to be kinetically unstable; their stability

is enhanced by structural crowding, which protects the coordination sites

of the metal. The 6-coordinate W(CH3)6 can be melted at 30 °C without

decomposition, whereas the 4-coordinate Ti(CH3)4 is subject to

decomposition at approximately –40 °C.

*Other ligands have direct metal–carbon σ-bonds (Table below). In

addition, there are many examples of metallacycles, complexes in which

organic ligands attach to metals at two positions, thereby incorporating

the metals into organic rings. The reaction below is an example of a

metallacycle synthesis. Metallacycles are important intermediates in

catalytic processes.

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*Carbene Complexes

Carbene complexes contain metal–carbon double bonds. First synthesized

in 1964 by Fischer, carbene complexes are known for the majority of

transition metals and for a wide range of carbene ligands, including the

simple carbene, :CH2. The majority of such complexes contain one or

two highly electronegative heteroatoms—such as O, N, or S— directly

attached to the carbene carbon. These are designated as Fischer-type

carbene complexes. Other carbene complexes contain only carbon and/or

hydrogen attached to the carbene carbon. First synthesized several years

after the initial Fischer carbene complexes, these have been studied

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extensively by Schrock and several others. They are sometimes

designated as Schrock-type carbene complexes, commonly referred to as

alkylidenes. Distinctions between Fischer- and Schrock-type carbene

complexes are summarized in Table below. We will focus primarily on

Fischer-type carbene complexes.

*The formal double bond in carbene complexes may be compared with

the double bond in alkenes. In the case of a carbene complex, the metal

must use a d orbital to form the π- bond with carbon.

*Carbene complexes having a highly electronegative atom such as O, N,

or S attached to the carbene carbon tend to be more stable than

complexes lacking such an atom. For example,

Cr(CO)5[C(OCH3)C6H5], with an oxygen on the carbene carbon, is

much more stable than Cr(CO)5[C(H)C6H5]. The stability of the

complex is enhanced if the highly electronegative atom can participate in

the π- bonding, with the result a delocalized, 3-atom π system involving a

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d orbital on the metal and p orbitals on the carbon and on the

electronegative atom. Such a delocalized 3-atom system provides more

stability to the bonding π electron pair than would a simple metal-to-

carbon π bond.

*The methoxycarbene complex Cr(CO)5[C(OCH3)C6H5] synthesized

via reacting phenyllithium with Cr(CO)6 to give the anion

[C6H5C(O)Cr(CO)5]-, which has two important resonance structures:

Alkylation by a source of CH3+, such as [(CH3)3O][BF4] or CH3I, gives

the methoxycarbene complex:

Evidence for double bonding between chromium and carbon is provided

by X-ray crystallography, which measures this distance at 204 pm,
compared with a typical Cr-C single-bond distance of approximately 220
pm.
*Carbyne (Alkylidyne) Complexes

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Carbyne complexes have metal–carbon triple bonds; they are formally

analogous to alkynes. Many carbyne complexes are now known;
examples of carbyne ligands include the following:

where R = aryl, alkyl, H, SiMe3, NEt2, PMe2, SPh, or Cl. Carbyne

complexes were first synthesized by chance as products of the reactions
of carbene complexes with Lewis acids. The methoxycarbene complex
Cr(CO)5[C(OCH3)C6H5] was found to react with the Lewis acids BX3
(X = Cl, Br, or I). First, the Lewis acid attacks the oxygen, the basic site
on the carbene:

The intermediate loses CO, with the halide coordinating trans to the

carbyne:

The best evidence for the carbyne nature of the complex is provided by

X-ray crystallography, which gives a Cr-C bond distance of 168 pm (for

X = Cl), considerably shorter than the 204 pm for the parent carbene

complex. The angle is, as expected, 180° for this

complex; however, slight deviations from linearity are observed for many

complexes in crystalline form, in part a consequence of crystal packing

effects.

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*Bonding in carbyne complexes may be viewed as a combination of a σ-

bond plus two π-bonds (Figure below). The carbyne ligand has a lone

pair of electrons in an sp hybrid on carbon; this lone pair can donate to a

suitable orbital on Cr to form a σ- bond. In addition, the carbon has two p

orbitals that can accept electron density from d orbitals on Cr to

form π bonds. Thus, the overall function of the carbyne ligand is as both a

σ donor and π acceptor. (For electron counting purposes, a :CR+ ligand

can be considered a 2-electron donor; it is usually more convenient to

count neutral CR as a 3-electron donor).

In some cases, molecules have been synthesized containing two or three

of the types of ligands discussed in this section (alkyl, carbene, and
carbyne).

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*Carbide and Cumulene Complexes

The first neutral carbide complex was a trigonal-bipyramidal ruthenium

complex (Figure below). The Ru-C distance in this complex is perhaps

longer than might be expected, 165.0 pm, only slightly shorter than the

comparable distance in the structurally similar ruthenium carbyne

complex, also shown.

*Calculations have indicated that bonds between transition metals and

terminal carbon atoms are quite strong, with bond dissociation enthalpies

comparable to those of transition-metal complexes with M≡N and M꞊O

bonds. In addition, the frontier orbitals of the carbide complex in Figure

above (where R = methyl) have many similarities to those of CO,

suggesting that such complexes may potentially show similar

coordination chemistry to the carbonyl ligand.

*Ligands with chains of carbon atoms that have cumulated (consecutive)

double bonds, designated cumulenylidene ligands, are also known. Such

metallacumulene complexes have drawn interest because of possible

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applications as 1-dimensional molecular wires and for use in nanoscale

optical devices. In recent years, complexes with 2- and 3-carbon chains

have also been developed as effective catalysts.

The longest cumulenylidene ligand reported to date is the

heptahexaenylidene complex shown in Figure below. As in the case of

extended organic pi systems, the difference in energy between the

HOMO and the LUMO decreases as the length of the cumulene ligand

increases.

*Carbon Wires: Polyyne and Polyene Bridges

The most widely studied types of these bridges have been the

polyynediyl bridges with alternating single and triple bonds and

polyenediyl bridges with alternating single and double bonds.

The bond conjugation (extended π system) is needed to enable electronic

communication between the metal atoms at the ends of the bridges;

saturated bridges or sections of bridges inhibit such communication.

Examples of structures containing polyyne and polyene bridges are in

Figure below.

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Organometallic Reactions
**Reactions Involving Gain or Loss of Ligands
Many reactions of organometallic compounds involve a change in metal

coordination number by a gain or loss of ligands. If the oxidation state of

the metal is retained, these reactions are considered addition or

dissociation reactions; if the metal oxidation state is changed, they are

termed oxidative additions or reductive eliminations. In classifying these

reactions, it is often necessary to determine oxidation states of the metals.

1- Ligand Dissociation and Substitution reaction

These reactions involved replace ligands such as carbon monoxide and
phosphines.
a- CO Dissociation
We previously mentioned carbonyl dissociation reactions, in which
CO may be lost thermally or photo chemically. Such a reaction
may result in rearrangement of the remaining molecule or
replacement of CO by another ligand:

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The second type of reaction shown above, involving ligand

replacement, is an important way to introduce new ligands into

complexes. Most thermal reactions involving replacement of CO by

another ligand, L, have rates that are independent of the concentration of

L; they are first order with respect to the metal complex. This behavior is

consistent with a dissociative mechanism involving slow loss of CO,

followed by rapid reaction with L:

The first step is rate limiting, and has the rate law Rate =

k1[Ni(CO)4]. Some ligand replacement reactions show more complicated

kinetics. Study of the following reaction

has shown that, for some phosphines, the rate law is:

The two terms in the rate law imply parallel pathways for the formation

of Mo(CO)5L. The first term is consistent with a dissociative mechanism:

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There is strong evidence that solvent is involved in the first-order

mechanism for the replacement of CO; however, because the solvent is in

great excess, it does not appear in the above rate law; this pathway

exhibits pseudo–first order kinetics. The second term is consistent with an

associative process, involving a bimolecular reaction of Mo(CO) 6 and L

to form a transition state that loses CO:

Formation of the transition state is the rate-limiting step in this

mechanism; the rate law for this pathway is

The overall rate of formation of Mo(CO)5L is the sum of the rates of the

unimolecular and bimolecular mechanisms, Rate1 + Rate2.

* Most CO substitution reactions proceed by dissociative mechanisms.

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b- Dissociation of Phosphine

Ligands other than carbon monoxide can dissociate, with the ease of

dissociation a function of the strength of metal–ligand bonding. The

metal–ligand bond strength depends on an interplay of electronic effects

(for example, the match of energies of the metal and ligand orbitals) and

steric effects (for example, the degree to which crowding of ligands

around the metal can reduce the strength of metal-ligand orbital overlap).

These steric effects have been investigated for many ligands but

especially for neutral donor ligands such as phosphines.

*The presence of bulky ligands results in crowding around the metal.

This can lead to more rapid ligand dissociation as a consequence of slight

elongation of metal–ligand bonds to relieve steric hindrance at the metal

center.

2- Oxidative Addition and C—H Bond Activation

These reactions involve an increase in both the oxidation state and the

coordination number of the metal. Oxidative addition (OA) reactions are

essential steps in many catalytic processes. The reverse reaction,

designated reductive elimination (RE), is also very important. These

reactions are described schematically by the following:

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*Oxidative addition reactions of square-planar d8 complexes are

ubiquitous; we will use one such complex, trans-Ir(CO)Cl(PEt3)2, to

illustrate these reactions.

*In next Figure , the iridium oxidation state increases from (I) to (III),

and the coordination number increases from 4 to 6. The new ligands add

in a cis or trans fashion, with their orientation a function of the

mechanistic pathway.

*The expansion of the coordination number of the metal brings the newly

added ligands into close proximity to the original ligands; this can enable

reactions to occur between them. Such reactions are encountered

frequently in the mechanisms of catalytic cycles.

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*Oxidative addition and reductive elimination reactions play key roles in

C—H activation reactions, where a strong C—H bond is cleaved by a

transition-metal complex. These are important reactions because they

permit unfunctionalized hydrocarbons to be transformed into complex

molecules. Bergman reported the following classic C—H reductive

elimination/oxidative addition sequence.

The first step involves reductive elimination of cyclohexane from a six-

coordinate Ir(III) complex (ML3X3) to afford a four-coordinate Ir(I)

intermediate (ML3X). Like most reductive eliminations, this first step

involves a decrease by two in both the oxidation state and coordination

number of the metal. The second step results in oxidation from Ir(I) to

Ir(III) as benzene oxidatively adds to the iridium center. Like most

oxidative additions, this second step involves an increase by two in both

the oxidation state and the coordination number of the metal.

**Cyclometallations

These are reactions that incorporate metals into organic rings.

Orthometallations, oxidative additions in which an ortho position of an

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aromatic ring becomes attached to the metal, are quite common. The first

(Figure below) example features oxidative addition in which the ortho

carbon to the phosphorus of a triphenylphosphine ligand and the

hydrogen originally in the ortho position add to iridium, resulting in a

four-membered ring involving the iridium center. Orthometallation is not

the favored pathway in the second reaction even though the platinum

reactant also has triphenylphosphine ligands. A five-membered ring is

formed instead by oxidative addition of a C—H bond of the naphthalene

substituent, concurrently with reductive elimination of methane. In these

reactions, the reactants are kinetic products that are converted to

cyclometallated thermodynamic products. These reactions are also

classified as C—H bond activations. The metal facilitates the cleavage of

C—H bonds.

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* Nucleophilic Displacement

Another class of reaction that can be classified as oxidative addition, is

nucleophilic displacement. Negatively charged organometallic complexes

often behave as nucleophiles in displacement reactions. For example,

-
[(η5-C5H5)Mo(CO)3] can displace iodide from methyl iodide:

This reaction results in formal oxidation of the metal (from Mo(0) to

Mo(II)) and the coordination number increases by 1 .

3-Reductive Elimination and Pd-Catalyzed Cross-Coupling

Reductive elimination is the reverse of oxidative addition. To illustrate

this distinction, consider the following equilibrium:

The forward reaction involves formal oxidation of the metal,

accompanied by an increase in coordination number; it is an OA. The

reverse reaction is an example of RE, which involves a decrease in both

oxidation number and coordination number.

Reductive elimination can result in the formation of a wide range of

bonds including H—H, C—H, C—C, and C—X (X = halide, amide,

alkoxide, thiolate, and phosphide).

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Reductive eliminations from palladium are of great interest because they

comprise an important step in Pd-catalyzed cross-coupling; Figure

below, (A generic Pd-catalyzed cross-coupling cycle.) provides a

generic catalytic cycle. Step 1 is oxidative addition of RX (R = alkyl,

aryl) to a Pd(0) reactant, resulting in a square planar Pd(II) complex. If

this product is cis (as shown), rapid cis–trans isomerization (step 2) is

likely to avoid having a strong donor R trans to another good σ donor

(L). Step 3 is transmetallation, a ligand substitution reaction, that

introduces ( = alkyl, aryl) to the Pd(II) center. Reductive

elimination of a C—C bond (step 5) requires the cis orientation of R and

, so a cis–trans isomerization is necessary (step 4) if the

transmetallation product is trans (as shown).

The reductive elimination reaction (step 5) generally proceeds faster as

the steric bulk imposed by L increases.

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*A series of C—S bond-forming reductive elimination reactions with

bidentate ligands (Figure below) with different bite angles illustrates this

trend. Bite angles are steric parameters specific to bidentate ligands. As

the bite angle increases, the bidentate ligand imposes increasing steric

hindrance when coordinated. The rate of dialkylsulfide reductive

elimination increases with the bite angle (Table below).

*The electronic properties of the ligands also have a large impact on the

rates of reductive elimination from Pd(II) complexes for the formation of

carbon–carbon and carbon–heteroatom bonds.

*Palladium-catalyzed cross-coupling reactions to form carbon–carbon

bonds have become extremely important tools in organic synthesis during

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the past several decades. In recognition of their work as pioneers in this

field, R. F. Heck, E.-I. Negishi, and A. Suzuki were awarded the Nobel

Prize in Chemistry in 2010.

*Table below provides representative examples of the types of Pd-

catalyzed cross-coupling reactions associated with these Nobel recipients

and two other major chemists in this field, K. Sonogashira and J. K.

Stille.

4-Sigma Bond Metathesis

All previously mentioned C—H bond activation examples exhibit the

classic characteristics of oxidative addition and involve metal centers

with eight valence electrons (Ir(I), Pd(II), Fe(0)). These metals have

relatively low oxidation states and are predisposed toward being able to

oxidize C—H bonds. Does this mean that complexes with metals in their

formally highest oxidation states are inherently unable to effect C—H

bond activation? It is fascinating that some d0 transition-metal complexes

are able to activate C—H bonds without any change in -oxidation state.

For example, consider the following classic reaction:

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

In this reaction, a C—H bond in methane is made, and a C—H bond of

benzene is cleaved, but the oxidation state of the scandium center remains

(+3). This class of reaction, which is not limited to early transition metals,

is called sigma-bond metathesis. In this mechanism, the metal is first

postulated to coordinate the bond to be activated in an η2 fashion,

followed by formation of a four-centered transition state that leads to an

exchange of ligands at the metal (Figure below).

General Sigma-Bond Metathesis Mechanism

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Organometallic chemistry…. (2016-first course-2017) …. Fourth Class

**Reactions Involving Modification of Ligands

1-Insertion Reactions

The reactions in Figure below may be designated as 1,1 insertions,

indicating that both bonds to the inserted molecule are made to the same

atom in that molecule. For example, in the second reaction, both the Mn

and CH3 are bonded to the sulfur of the inserted SO 2.

Examples of 1,1 Insertion Reactions

*In 1,2 insertions, bonds to the inserted molecule are made to adjacent

atoms. For example, in the reaction of HCo(CO)4 with

tetrafluoroethylene (next Figure), the product has the Co(CO)4 group

attached to one carbon and the H attached to the neighboring carbon.

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2-Carbonyl Insertion (Alkyl Migration)

Carbonyl insertion, the reaction of CO with an alkyl complex to give an

acyl [-C(=O)R] product, has been well-studied. The reaction of

CH3Mn(CO)5 with CO is an excellent example:

*The insertion of CO into a metal–carbon bond in alkyl complexes is of

particular interest for its potential applications to organic synthesis and

catalysis, and its mechanism deserves careful consideration.

*From the net equation, we might expect that the CO inserts directly into

the Mn-CH3 bond. However, other mechanisms are possible that would

give the overall reaction stoichiometry and involve steps other than the

insertion of an incoming CO. Three plausible mechanisms have been

suggested:

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* The stoichiometry of a reaction, can be used to predict how much

reactant is needed to create a certain amount of product or to predict how

much of the product will be formed from a certain amount of reactant.

Mechanism 1: CO Insertion

Direct insertion of CO into a metal–carbon bond.

Mechanism 2: CO Migration

Migration of a CO ligand to give intramolecular CO insertion. This would

yield a 5-coordinate intermediate, with a vacant site available for

attachment of an incoming CO.

Mechanism 3: Alkyl Migration

In this case, the alkyl group would migrate, rather than the CO, and

attach itself to a CO cis to the alkyl. This would also give a 5-coordinate

intermediate with a vacant site available for an incoming CO.

* These mechanisms are described schematically in Figure below. In

both mechanisms 2 and 3, the intramolecular migration is considered to

occur to one of the migrating group’s nearest neighbors, located in cis

positions.

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Possible Mechanisms for CO Insertion Reactions

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