Module - 23.

d - block Elements

Introduction:

The elements that lie in between s-block and P-block are the d-block
elements. These elements are called transition elements as they show
transitional properties between s and p-block elements. These elements
contain partially filled d-orbitals and hence they are called as d-block
elements. The general electronic configuration of d-block elements is
(n-1) d1-10ns1-2.The d-block comprises of 3d, 4d, 5d and 6d series of
elements.

First transition series

This is also called as 3d series which corresponds the filling of 3d orbital. It starts
from scandium whose atomic number is 21 and includes 10 elements till zinc
whose atomic number is 30.

Second transition series

This is also called as 4d series which corresponds the filling of 4d orbital. It starts
from yttrium whose atomic number is 39 and includes 10 elements till cadmium
whose atomic number is 48.

Third transition series

This is also called as 5d series which corresponds the filling of 5d orbital. The first
element of this series is lanthanum whose atomic number is 57 and includes 9
elements from hafnium whose atomic number is 72 to mercury whose atomic
number is 80

Fourth transition series

This is also called as 6d series which corresponds the filling of 6d orbitals.

General trends in properties of first row of transition metals:

Electronic configuration of the elements of first transition series:

Element Atomic number Electronic configuration:

Scandium 21 1s2 2s2 2p6 3s2 3p6 4s2 3d1

Titanium 22 1s2 2s2 2p6 3s2 3p6 4s2 3d2

Vanadium 23 1s2 2s2 2p6 3s2 3p6 4s2 3d3

Chromium 24 1s2 2s2 2p6 3s2 3p6 4s1 3d5

Manganese 25 1s2 2s2 2p6 3s2 3p6 4s2 3d5

Iron 26 1s2 2s2 2p6 3s2 3p6 4s2 3d6

Cobalt 27 1s2 2s2 2p6 3s2 3p6 4s2 3d7

Nickel 28 1s2 2s2 2p6 3s2 3p6 4s2 3d8

Copper 29 1s2 2s2 2p6 3s2 3p6 4s1 3d10

Zinc 30 1s2 2s2 2p6 3s2 3p6 4s2 3d10

Chromium and copper exhibit anomalous electronic configurations due to

the following reasons.
 Electronic configuration of chromium (Z = 24) is 1s2 2s2 2p6 3s2 3p6 4s1 3d5

Electronic configuration of copper (Z = 29) is 1s2 2s2 2p6 3s2 3p6 4s1 3d10

In case of half filled sub shells there is a maximum number of unpaired

electrons in different orbitals. In such cases, the inter electronic repulsions
are minimum and there is a maximum possibility of exchange or
delocalization of electrons, which further decreases the energy and
increases the stability.

Metallic character:

Most of the transition elements of the first row form metallic bonds due to
the presence of incomplete outermost energy level. So, all the transition
elements exhibit metallic characters. The strength of the metallic bond
depends upon the number of unpaired d-electrons. As the number
increases the strength also increases. Due to the absence of unpaired
electrons 'Zn' is not a hard metal.

Ionization energy:

The ionization energies of first row elements gradually increases with

increase in atomic number. The ionization energy of Zn is very high than all
the other metals which is due to its fully filled d-orbital. The third ionization
energy of Mn is very high than the others.

Ionic radii:

In the first row transition elements the ionic radii decrease with increase in
atomic number. The value of ionic radii also depends on the oxidation state
of metals. As the oxidation state increases the ionic radius decreases and as
the oxidation state decreases the ionic radius increases.

Oxidation states:

d – block elements shows more than one oxidation states due to availability
both ns and (n – 1)d electrons in the compound formation. The lowest
oxidation state is exhibited by using the s – electrons in the outermost orbit
 and the maximum oxidation state is given by the sum of the outer
s – electrons and unpaired d – electrons.

The maximum oxidation state in first series is +7 exhibited by manganese.

In second and third transition series, the maximum oxidation sate is +8 in
Ruthenium and osmium shown in their oxides.

In a given series of d – block elements the oxidation state increases upto

nearly middle element and then decreases. The most stable oxidation state
in all the elements of 3d – series is +2.

Variable oxidation states of 3d series

I series Sc Ti V Cr Mn Fe Co Ni Cu Zn

3d 4s23d1 4s23d2 4s23d3 4s13d5 4s23d5 4s23d6 4s23d7 4s23d8 4s13d10 4s23d10
I

II II II II II II II II II II

III III III III III III III

IV IV

VI VI

VII

Colour:

Transition metal ions are generally coloured due to the presence of

unpaired d – electrons. Which absorb light from the visible region and thus move
to higher energy level. Therefore, one of the colours of the visible spectrum is
absorbed and the transition metal ion gets the complementary colour. The
transition metal ion with completely filled d – orbitals are colourless. For example
Zn+2, Cd+2 and Hg+2 are colourless. The colour of transition metal ions is due to
excitation of d – orbitals of lower energy to the d – orbitals of higher energy. Since
they are completely filled d – orbitals in Zn+2 (3d10), Cd+2 (4d10) and Hg+2 (5d10)
ions, these are colourless. The energy required to excite a d – electron of
transition metal ion is small. Hydrated copper (+2) ion i.e. Cu(H2O)6+2 absorbs red
colour from the visible light appears blue, the complementary colour of red. Thus
Cu(H2O)6+2 appear blue.

Example:

Ion Colour
Cu+2 Blue

Fe+2 Pale green

Fe+3 Yellow

Cr+3 Green

Mn+2 Pink

Zn+2 Colourless

Cu+2 ions are coloured and are paramagnetic:

Electronic configuration of Cu+2 ion = 1s2 2s2 2p6 3s2 3p6 3d9

Cu+2 ion contains one unpaired d – electron. So it is coloured and

paramagnetic.

Magnetic properties:

Those substances which are weakly attracted by the magnetic field are
called paramagnetic substances. This magnetic character arises due to the
presence of unpaired electrons. Most of the transition elements and their
ions contain unpaired d – electrons. So they are paramagnetic substances.

Example:

Ti+3, Cu+2, Sc+2 they have unpaired electrons

Those substances which are repelled by the magnetic field are called
diamagnetic substances. This magnetic character arises due to the presence
of paired electrons. Transition metal ions which contain paired electrons
show diamagnetic substances.

Example:

Ti+4, Cu+, Zn+2 have all the electrons completely paired.

Those substances which are strongly attracted by the magnetic field are
ferromagnetic substances. These also contain unpaired electrons. Iron,
cobalt and nickel are ferromagnetic substances.

Catalytic property:

Many d – block elements and their compounds act as catalysts in chemical

reactions. This property may be either due to their variable valency which
enables them to form unstable intermediate compounds or due to
providing suitable reaction surfaces.

Some catalysts used in the industries.

Process Catalyst
Hydrogenation of oils Ni

Synthesis of ammonia by Haber’s process Fe

Synthesis of nitric acid by Ostwald’s process Pt

Synthesis of sulphuric acid by contact process V2O5

Complex formation:

d – block metal ions having a great tendency to form complexes due to

their small sizes, high charges and due to the presence of vacant
d – orbitals.

The bonds involved in the formation of complexes are co – ordinate bonds.

So complexes are called co – ordinate compounds. In complexes the groups
which donate the electron pairs are called ligands and the metal ions which
accept the electron pairs are called central metal ions. The central metal
ions and the ligands are represented by a square bracket and other ions are
 represented outside the bracket. The square bracket part is a complex ion
and it involves as a single unit in chemical reactions.

Example:

1. K3 [Fe (CN)6] potassium ferricyanide.

2. [Cr (NH3)6]Cl3 hexamminechromium (III) chloride.
In a series the stability of complexes increases with an increase in the
atomic number of the elements and in a particular oxidation state with
decrease in the size of its atoms. When the d – block metal atom
exhibits more than one oxidation state, the highest valent ion forms
more stable complex.

Redox potential of d – block elements:

Standard reduction potentials of 3d series obtained by the reduction of

M+ 2 ions to M are given below.

M+2 + 2e- → M

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Reduction
potential – 2.1 – 1.6 – 1.2 – 0.91 – 1.18 – 0.44 – 0.28 – 0.25 + 0.34 + 0.76
(Volts)

When we observe the values in the table, except copper the remaining
elements have higher negative values than standard hydrogen potential
(zero).Hence these elements are easily oxidized to give ions.

M → M+2 + 2e-.

Review questions:

Example set:

1. Transition elements are ______ block elements.

a. s
b. p
 c. d
d. f

Solution: c)

2. The first transition element in the 3d series is:

a. scandium
b. chromium
c. nickel
d. copper

Solution: a)

3. The property, which is not characteristic of transition metals, is:

a. Variable oxidation states
b. Tendency to form complexes
c. Formation of colored compounds
d. Electro negative behaviour

Solution: d)

4. Which of the following elements exhibits largest number of oxidation states?

a. Zn
b. V
c. Mn
d. Ni

Solution: c)

5. Transition metals show paramagnetism due to

a. characteristic configuration
b. high lattice energy
c. variable oxidation states
d. unpaired electrons

Solution: d)

6. How do the following properties very in the first transition series?

 a. Atomic size
b. Stability of various oxidation states
c. Ionization energy

Solution:

7. What are d – block elements?

Solution:

The elements in which differentiating electron is accommodated in the d –

subshell are called d – block elements.

8. Name three characteristic properties of d – block elements.

Solution:

a. Formation of coloured compounds

b. Formation of complex compounds
c. Paramagnetic in nature
9. Name two elements of 3d – series which show anomalous electronic
configuration.

Solution:

Chromium, copper

Problem set:

1. The general electronic configuration of transition elements is

a. (n – 1) d1 – 5
b. (n – 1) d1 – 10 ns1
c. (n – 1) d1 – 10 ns1 or 2
d. None

Solution: c)

2. Chromium has the electronic configuration

a. 3s2 3p6 3d4 4s2
 b. 3s2 3p6 3d5 4s1
c. 3s2 3p6 3d6
d. None of these

Solution: b)

3. Which of the following has the maximum number of unpaired d – electrons?

a. Zn
b. Fe2+
c. Ni3+
d. Cu+

Solution: b)

4. Why CuSO4 is blue while ZnSO4 is white?

Solution:

Cu2+ in CuSO4 has [Ar] 3d9 4s0 configuration. It can undergo d – d transition. It
absorbs red light of the visible region and hence CuSO4 appears blue. Blue is
complimentary colour of red. In ZnSO4, Zn2+ has 3d10 4s0 configuration. It
cannot undergo d – d transition, hence, they are soft in nature.
5. Transition elements form alloys easily. What is the reason?

Solution:

Nearly same atomic radii.

6. Which ions of first transition series show highest paramagnetism?

Solution:

Fe3+ and Mn2+.

Exercise questions:

1. What is the magnetic moment of K3 [FeF6]?

a. 5.91 B.M
b. 4.89 B.M
 c. 3.87 B.M
d. 6.92 B.M
2. Why Fe+3 compounds are more stable?
3. Why transition metals and their compounds act as catalysts.
4. Why Hg2+ and Hg 2+2 salts are colourless.
5. Cu are paramagnetic while Cu+ salts are diamagnetic in nature.
2+

6. Predict the spin only magnetic moment for

a. Fe2+
b. Mn2+
c. Cr6+
d. Cu+

Solutions:

1. a)
2. 3d5 configuration, i.e., all the five orbitals are singly occupied.
3. Because of the availability of d – orbitals they can easily form intermediate
products which are activated. The sizes of transition metal atoms and ions are
also favourable for transitory complex formation with the reactants.
4. Hg2+ and Hg 2+ 10
2 salts have 5d configuration, i.e. there is no d – d transition,
hence colourless.
5. Cu+2 configuration is 3d9 (one orbital is singly occupied) – paramagnetic; Cu+
configuration is 3d10 (all orbitals are doubly occupied) – diamagnetic.
6.
Ion Electronic No. of unpaired Magnetic
configuration electrons moment
2+ 6 0
a. Fe [Ar]3d 4s 4 4.90 BM
2+ 5 0
b. Mn [Ar]3d 4s 5 5.96 BM
6+ 0 0
c. Cr [Ar]3d 4s 0 0 BM
+ 10 0
d. Cu [Ar]3d 4s 0 0 BM
 Co-ordination Compounds
Module 24.1: Introduction, ligands, co-ordination number,
IUPAC nomenclature
Double salts or lattice compounds:

The addition compounds which are stable in solid state only but are broken down
into individual constituents when dissolved in water are called double salts or
lattice compounds. Their solutions have the same properties as the mixture of
individual components. For example, when Mohr’s salt, FeSO4.(NH4)2SO4.6H2O, is
dissolved in water, it exhibits the properties of FeSO4 and (NH4)2SO4, i.e., they
produce Fe2+, 𝑁𝐻4+ , and 𝑆𝑂42− ions in the solution. Thus, each ion has its identity
in the double salt.

Carnallite: KCl.MgCl2.6H2O;

Potash alum: K2SO4. Al2(SO4)3.24H2O etc. are the examples of double salts.

Co-ordination or complex compounds:

The addition compounds in which some of the constituent ions or molecules lose
their identity and when dissolved in water they do not break up completely into
individual ions, are called co-ordination compounds or complex compounds. The
properties of their solutions are different from those of their constituents. When
crystals of CuSO4.4NH3 are dissolved in water there is hardly any evidence for the
presence of Cu2+ ions or ammonia molecules. A new ion [Cu(NH3)4]2+ is furnished
in which ammonia molecules are directly linked with the metal ion. Similarly, the
aqueous solution of Fe(CN)2.4KCN does not give tests of Fe2+ and CN- ions but
gives the test for a new ion [Fe(CN)6]4-. The ions [Cu(NH3)4]2+ and [Fe(CN)6]4- are
called complex ions.
Thus, a co-ordination or complex compound may be defined as a molecular
compound that results from the combination of two or more simple, stable,
molecular compounds and retains its identity in the solid as well as in dissolved
state.

Definition of the terms used in coordinate compounds:

1. Central ion or centre of coordination:

The cation to which one or more neutral molecules or anions are attached is
called the central metal ion of coordination. Since, the central ion acts as an
acceptor and thus, has to accommodate electron pairs donated by the donor
atom of ligand, it must have empty orbitals. This explains why the transition
metals, having empty d – orbitals form coordination compounds very readily.

Thus, in the complexes [Ni(NH3)6]2+ and [Fe(CN)6]3-, Ni2+ and Fe3+ ions respectively
are the central metal ions.

2. Ligands:

The neutral molecules; anions or cations which are directly linked with central
metal atom or ion in a complex ion are called ligands. The ligands are attached to
the central metal ion or atom through coordinate bonds or dative linkages. Free
ligands have at least one electron pair that is not engaged in bonding. Some
examples are:

The ligands act as a donor as it donates one or more electron pairs to the central
metal atom or ion which acts as an acceptor. The ligands are thus Lewis bases and
central metal ions are Lewis acids and their union involves following two things.
a. Ligands should have lone pairs of electros which can be donated to the central
metal ion or atom.
b. The central atom or ion should have vacant orbital’s of nearly equivalent
energy to accommodate the electrons donated by ligands. This condition is
easily fulfilled by atoms or ions of transition metals.

Types of ligands:

Ligands can be of following types depending on the number of donor atoms

present in them.

i. Mono or unidentate ligands:

They have one donor atom, i.e., they supply only one electron pair to central
metal atom or ion. F-, Cl-, Br-, H2O, NH3, CN-,𝑁𝑂2− , OH-, CO etc. are examples of
monodentate ligands.
ii. Bidentate ligands:
Ligands, which have two donor atoms and have the ability to link with the
central metal ion at two positions, are called bidentate ligands. Some
examples are:

iii. Tridentate ligands:

The ligands having three donor atoms are called tridentate ligands. Examples
are:
 Similarly polydentate ligands are ligands having more than two donor atoms.
iv. Chelating ligands:
A bidentate or a polydentate ligands is known as a chelating ligands if, on
coordination, it results in the formation of a closed or cyclic ring structure. The
complexes, thus formed are called chelates. The word chelate has been
derived from the Greek word chelate meaning claw. The complex formed by
Cu2+ ion with ethylenediamine is an example of a chelate.

The following are the characteristics of chelates:

a. Chelating ligands form more stable complexes than monodentate ligands.

This is called chelating effect, all types of polydentate ligands can act as
chelating ligands.
b. The chelates containing 5 or 6 membered rings including metal atom are
comparatively more stable. Chelating ligands which do not contain
unsaturated groups (double bonds), in general, form five membered stable
complexes while chelating ligands having unsaturated groups (double
bonds) form six membered stable complexes.
c. Ligands with larger groups form more unstable rings than with smaller
groups due to steric hindrance.
3. Co-ordination number:

The total number of ligands attached to the central ion in a complex compound is
known as the coordination number of that ion. Thus, the coordination numbers of
silver and copper ions in the complexes [Ag(NH3)2]+ and [Cu(H2O)4]2+ are 2 and 4
respectively.

4. Co-ordination sphere:

The central metal atom and the ligands directly attached to it are collectively
termed as the coordination sphere. Coordination sphere is written inside square
bracket, as for example [Co(NH3)6]3+. Remember that the central metal atom and
the ligands inside the square bracket behave as a single entity.

Thus, the various terms used in a coordination compound can be illustrated as

below:

5. Oxidation number:

It is a number (numerical value) which represents the electric charge on the

central metal atom of a complex ion. For example, the oxidation number of Fe, Co
and Ni in [Fe(CN6)]4-, [Co(NH3)6]3+ and Ni(CO)4 is +2, +3 and 0 respectively.

Complex ion:

A complex (coordinate) ion is an electrically charged or a neutral species formed

by the combination of a central cation with more than one ligand species.
The charge carried by a complex ion is the algebraic sum of charges carried by the
central ion and the ligands coordinated to it. Charges of some complex
compounds are given below:

S.No Complex compound (ion) Charge on complex ion

(i) [Cu(NH3)4]2+ (+2) of Cu + (0) of NH3
 Net charge = +2
(ii) [Fe(CN)6]4- (+2) of Fe + (-6) of 6 CN
 Net charge = -4
(iii) (Co(NH3)5Cl]2+ (+3) of Co + (0) of NH3 + (-1) of Cl
 Net charge = +2
(iv) [Co(NH3)3Cl3] (+3) of Co + (0) of NH3 + (-3) of Cl
 Net charge = 0

Nomenclature of Co-ordination compounds (IUPAC system):

The following rules are adopted for naming all types of coordination compounds:

1. If a coordination compound is ionic, the name of cation is given whether or not

it is the complex ion followed by the name of the anion just like naming a
simple salt. The names of cation and anion are separated by a space.
2. Within a complex ion, the ligands are named first followed by the metal ion

Naming of the ligands:

a. Anionic ligands ending with – ide are named by replacing – ide with suffix – o
or replacing – e by – o.
Anion Symbol Name as ligand
-
Chloride Cl Chlorido
Bromide Br- Bromido
Cyanide CN- Cyano
Oxide O2- Oxo
2−
Peroxide 𝑂2 Peroxo
-
Hydroxide OH Hydroxo
2-
Sulphide S Sulphido
−
Amide 𝑁𝐻2 Amido
Nitride N3- Nitrido
Phosphide P3- Phosphido

Ligand whose names end in – ite or – ate become – ito or – ato, i.e., by
replacing the ending – e with – o.

Anion symbol Name of the ligand

Carbonate 𝐶𝑂32− Carbonato
Oxalate 𝐶2 𝑂42− Oxalato
Sulphate 𝑆𝑂42− Sulphato
Nitrate 𝑁𝑂3− Nitrato
Sulphite 𝑆𝑂32− Sulphito
Acetate CH3COO- Acetato
Nitrite ONO- (bonded through oxygen) Nitrito – O
𝑁𝑂2− (bonded through nitrogen) Nitrito – N or Nitro

b. Neutral ligands are called with the same names as their neutral molecules or
with their special names, e.g.,
H2O Aquo (Aqua) NH3 Ammine
CO Carbonyl; NO Nitrosyl;
CS Thiocarbonyl; NS Thionitrosyl
c. Positively charged ligands have suffix – ium.
NH2 - 𝑁𝐻3+ Hydrazinium; 𝑁𝑂2+ Nitronium
d. If the number of a particular ligand is more than one in the complex ion, the
number is indicated by using Greek prefixes such as di, tri, tetra, penta, hexa
etc.
e. When more than one ligand is present, they are named in alphabetical order
without separation by hyphen.
3. The oxidation state of the central metal is shown by Roman numerical in
bracket immediately following its name.
4. Complex positive ions and neutral coordination compounds have no special
ending.
5. Complex negative ions always end in the suffix – ate. In most of the cases, the
suffix – ate is fixed to names of the metals.
Name of components present in coordination sphere are written continuously
without a gap, e.g.,
K3[Fe(CN)5NO] potassium pentacyanonitrosylferrate (II)

Some names of the metals in the anionic complexes are given below.
Element Metal as named in ionic complex
Cobalt Cobaltate
Nickel Nickelate
Chromium Chromate
Iron Ferrate
Copper Cuprate
Silver Argentate
Lead Plumbate

6. The name of the neutral coordination compound is given in one word only as
the name of Ni(CO)4 is tetracarbonylnickel (0). The following examples will
make the rules more clear.
Coordination compounds containing complex cations:

[Pt(NH3)6]Cl4 Hexaammineplatinum(IV) chloride

[CO(NH3)4(H2O)Cl]Cl Tetraammineaquochloridocobalt(III) chloride

[Fe(H2O)4(C2O4)]2SO4 Tetraaquooxalatoiron(III) sulphate

[Ag(NH3)2]Cl Diamminesilver(I) chloride

Coordination compounds containing complex anions:

K4[Fe(CN)6] Potassium hexacyanoferrate(II)

K3[Fe(CN)6] Potassium hexacyanoferrate(III)

Na[Ag(CN)2] Sodium dicyanoargentate(I)

Na3[Co(NO2)6] Sodium hexanitrocobaltate(III)

K3[Fe(CN)5NO] Potassium pentacyanonitrosylferrate(II)

Coordination compounds containing complex cations and anions:

[Cr(NH3)6][Co(CN)6] Hexaamminechromium (III), hexacyanocobaltate (III)

[Pt(NH3)4][CuCl4] Tetraammineplatinum (II), tetrachloroidocuprate (II)

Non-ionic coordination compounds:

Fe(CO)5 Pentacarbonyliron (0)

[Co(NO2)3(NH3)3] Triamminetrinitrocobalt (III)

Writing the formula of a coordination compound from its IUPAC name:

Following rules are followed in writing the formula of a coordination compound:

1. Formula of the cation whether simple or complex is written first followed by

that of an anion
2. The coordination sphere is written in square brackets
3. The following sequence of symbols within the coordination sphere is followed:
i. Metal atom
ii. Anionic ligands
iii. Neutral ligands
iv. Cationic ligands
a. If there are number of ligands of same type (anionic, neutral or cationic),
they are listed alphabetically according to first alphabet of their names. For
example if 𝑁𝑂3− , 𝑆𝑂4− , OH-, Br- etc., are present, they are written as Br-,
𝑁𝑂3− , OH- and 𝑆𝑂42− .
When two ligands have same donor atom, the ligands with fewer such
atoms is cited first followed by the ligand having more atoms. For example,
𝑆𝑂42− , precedes 𝑆2 𝑂32− .
When the numbers of defining atoms are same, subsequent symbol decides
the sequence. For example, 𝑁𝐻2− precedes NO2 because H comes before O.
4. Polyatomic ligands are enclosed in parentheses but all ligands are formulated
without any space in between
5. The number of cations or anions to be written in the formula is calculated on
the basis of total negative charge on the anion, as the complex as a whole is
electrically neutral.
6. Sometimes abbreviations for certain ligands are used in parentheses instead of
their structural formulae. For example,
(en) ethylenediamine (ethane – 1, 2 – diamine)
(dien) diethylenetriamine
(trien) triethylenetetraamine
(edta or EDTA) ethane – 1, 2 – diamine tetraacetato
(dmg) dimethylglyoximato

Few examples are given here to explain the above rules.

Example 1:

Trichlorotriamminecobalt(III)

The metal complex is a neutral substance. The name of the central metal is
written first. Its oxidation state, then the ligands and their numbers are written.

Therefore the formula is written as [CoIII(NH3)3(Cl3)]

Example 2:

Tetramminecopper(II) hydroxide. The complex is a cationic complex. The formula

of the cation is written in the same order as in neutral complex. i.e. the central
metal, its oxidation state; ligands and their numbers.

Therefore [CuII(NH3)4]+2

The name of the anion only is given and not its number. Therefore hydroxide. The
number is inferred from the oxidation state of the complex species.

Therefore complete formula is [Cu(NH3)4](OH)2

Example 3:

Potassium tetrachloropalatinate(II)
The complex is an anionic complex

The cation is potassium. From the oxidation state of the complex anion, the
number of cations is 2.

The anion, obtained by applying the above procedure, is [PtII(Cl4)]-2

Therefore complete formula is K2[PtCl4]

Assignment Questions:

1. Mention which of the following substances is a double salt and which is a

complex compound?
a. Potash alum
b. Carnallite
c. Mohr’s salt
d. Potassium ferricyanide
2. Define the terms
a. Ligand
b. Chelate
3. Give the coordination number of the metal in the following compounds
a. [Ag(NH3)2]Cl
b. [Cu(H2O)4]SO4
c. K4[Fe(CN)6]
d. [Pt(en)3]Cl4
4. Write the names of the following complexes
a. Ag[NH3]2Cl
b. [Co(en)2Cl2]+
c. K4[Fe(CN)6]

Example Set:

1. Oxidation state of Fe in K4[Fe(CN)6] is

a. +2
b. +3
c. -2
 d. -3

Solution: a)

2. All ligands are

a. Lewis acids
b. Lewis bases
c. Neutral
d. Both a) and b)

Solution: b)

3. The number of ions formed in aqueous solution by the compound

[Co(NH3)4Cl2]Cl is
a. 2
b. 3
c. 4
d. 7

Solution: a)

4. [Co(NH3)6]Cl3 is called
a. Hexamminecobalt(III) chloride
b. Aminocobalt chloride(III)
c. Cobalt chloride hexammine
d. Hexammine tricobalt chloride

Solution: a)

5. Explain the terms co-ordination sphere and oxidation number of a central

metal atom.

Solution:

Coordination sphere: The central metal atom and the ligands directly attached to
it are collectively termed as the coordination sphere. Coordination sphere is
written inside square bracket, as for example [Co(NH3)6]3+. Remember that the
central metal atom and the ligands inside the square bracket behave as a single
entity.

Thus, the various terms used in a coordination compound can be illustrated as

below:

Oxidation number:

It is a number (numerical value) which represents the electric charge on the

central metal atom of a complex ion. For example, the oxidation number of Fe, Co
and Ni in [Fe(CN6)]4-, [Co(NH3)6]3+ and Ni(CO)4 is +2, +3 and zero respectively

Determination of oxidation number and coordination number of a metal atom or

ion in a complex is similar to the calculation of oxidation states in the compounds
as we know it from earlier studies.

6. State the principles involved in the nomenclature of co-ordination compounds

Solution:

Nomenclature of co-ordination compounds (IUPAC system):

The following rules are adopted these days for naming all types of coordination
compounds:

1. If a coordination compound is ionic, the name of cation is given whether or not

it is the complex ion followed by the name of the anion just like naming a
simple salt. The names of cation and anion are separated by a space.
2. Within a complex ion, the ligands are named first followed by the metal ion
a. Neutral ligands are called with the same names as their neutral molecules or
with their special names, e.g.,
H2O Aquo (Aqua) NH3 Ammine
CO Carbonyl; NO Nitrosyl;
CS Thiocarbonyl; NS Thionitrosyl
b. Positively charged ligands have suffix – ium.
NH2 - 𝑁𝐻3+ Hydrazinium; 𝑁𝑂2+ Nitronium
c. If the number of a particular ligand is more than one in the complex ion, the
number is indicated by using Greek prefixes such as di, tri, tetra, penta, hexa
etc.
d. When more than one ligand is present, they are named in alphabetical order
without separation by hyphen.
3. The oxidation state of the central metal is shown by Roman numerical in
bracket immediately following its name.
4. Complex positive ions and neutral coordination compounds have no special
ending.
5. Complex negative ions always end in the suffix – ate. In most of the cases, the
suffix – ate is fixed to names of the metals.

7. Write a short note on complex compounds.

Solution:

Complex compounds:

The addition compounds in which some of the constituent ions or molecules lose
their identity and when dissolved in water they do not break up completely into
individual ions, are called coordination compounds or complex compounds. The
properties of their solutions are different from those of their constituents. When
crystals of CuSO4.4NH3 are dissolved in water there is hardly any evidence for the
presence of Cu2+ ions or ammonia molecules. A new ion, [Cu(NH3)4]2+, is furnished
in which ammonia molecules are directly linked with the metal ion. Similarly, the
aqueous solution of Fe(CN)2.4KCN does not give tests of Fe2+ and CN- ions but
gives the test for a new ion, Fe(CN)6]4-. The ions [Cu(NH3)4]2+ and [Fe(CN)6]4- are
called complex ions.

Thus, a coordination or complex compound may be defined as a molecular

compound that results from the combination of two or more simple, stable,
molecular compounds and retains its identity in the solid as well as in dissolved
state.

Problem Set:

1. The IUPAC name of [Cr(NH3)4Cl2]NO3 is

a. Tetra amino dichloro chromium nitrate
b. Tetra amino dichloro chromium (II) nitrate
c. Tetra amminedichlorochromium(III) nitrate
d. Tetra amino dichloro chromium (II) nitrate

Solution: c)

2. EDTA is a ___ ligand

a. Monodentate
b. Hexadentate
c. Bidentate
d. Tridentate

Solution: b)

3. K3[Al(C2O4)3] is called
a. Potassium alumino oxalate
b. Potassium alumino (III) oxalate
c. Potassium trisoxalatoaluminate(III)
d. Potassium trioxalato aluminate (III)

Solution: c)
4. The IUPAC name for [Co(NH3)6][Cr(CN)6] is
a. Hexamminecobalt(III) hexacyano chromate(III)
b. Hexacyano chromium, cobalt hexa ammine (VI)
c. Hexa ammine cobalt (III) hexa cyano chromium (VI)
d. Hexa cyano chromium (III) hexa amine cobalt (III)

Solution: a)

5. Distinguish between double salt and complex compound.

Solution:

Double salt Complex compound

1. It is formed by combination of 1. It is formed by combination of two
two salts. They lose their salts which have lost their identity
identity when dissolved in water after union

Carnalite is dissolved in water to

It is dissolved in water to give K+ and
give Mg+2, K+ and Cl- which
[Fe(CN)6]4- ions. Here Fe+2 and CN- ions
answer their tests
Other examples are
Other examples are
2. Potash alum
2. [Co(NH3)6]Cl3
3. Cryolite
3. [Ni(CN)4]2-

6. What is the coordination number of the central metal ions in the following
complexes
a. [Cu(NH3)4]+2
b. [Fe(C2O4)3]3-
c. [Pt(en)2]Cl2
d. [Mo(CN)8]4-
e. [Fe(EDTA)]-
f. [Pd(H2O)2(ONO)2I2]

Solution:

a. NH3 is a monodentate ligand

 No. of points of attachment with Cu2+ = 4 × 1 = 4
C.N of Cu+2 = 4

b. 𝐶2 𝑂42− is a bidentate ligand

No. of points of attachment Fe+3 = 3 × 2 = 6
C.N of Fe+3 = 6

c. “en” is a bidentate ligand and Cl- is a monodentate ligand

No. of points of attachment with Pt+2 = 2 × 2 + 2 × 1 = 6
C.N of Pt+2 = 6

d. CN- is a monodentate liquid

No. of points of attachment with Mo4+ = 8 × 1 = 8
C.N of Mo4+ = 8

e. EDTA is a hexadentate liquid

No. of points of attachment with Fe+3 = 6 × 1 = 6
C.N of Fe+3 = 6

f. No. of points of attachment with Pd+4 = 2 × 1 + 2 × 1 + 2 × 1 = 6

C.N of Pd+4 = 6

Exercise Questions:

1. The IUPAC name of [Ni(NH3)4][NiCl4] is

a. Tetrachloronickel(II) tetramminenickel (II)
b. Tetramminenickel (II) tetrachloronickel (II)
c. Tetramminenickel(II) tetrachloronickelate(II)
d. Ttrachloronickel (II) tetrachloronickelate (0)
2. The correct structure of ethylenediaminetetraacetic acid (EDTA) is
a.

HOOC – CH2 CH2 – COOH

N – CH = CH – N
HOOC – CH2 CH2 – COOH
 b.

HOOC COOH
N – CH2 – CH2 – N
HOOC COOH

c.
HOOC – CH2 CH2 – COOH
N – CH2 – CH2 – N
HOOC – CH2 CH2 – COOH

d. COOH
HOOC – CH2 CH2 H
N – CH – CH – N
H CH2 – COOH
CH2
HOOC

3. What is meant by unidentate, bidentate and ambidentate ligands? Give two

examples for each.
4. Specify the oxidation number of the metals in the following coordination
entities.
a. [Co(H2O)(CN)(en)2]2+
b. [Co(Br)2(en)2]2+
c. [PtCl4]2-
d. K3[Fe(CN)6]
e. [Cr(NH3)3Cl3]
5. Write down the IUPAC names of the following compounds.
a. [Co(NH3]5(ONO)]Cl2
b. K3[Cr(CN)6]
6. Write the formulae of the following complexes
a. Pentammine chlorocobalt (III) ion
b. Lithium tetrahydrogen aluminate (III)
7.
8. 7.
9.

Identify A and B. Write the IUPAC names of A and B.

8. Write down the IUPAC names of the following compounds:
I. [Co(NH3)5ONO]Cl2
II. K3[Cr(CN)6]
III. [Cr(NH3)5CO3]Cl
9. Compare qualititatively the first and second ionization potentials of copper
and zinc. Explain the observation.
10.Write the IUPAC name of the compound [Cr(NH3)5(NCS)][ZnCl4]. Is this
compound coloured?
11.Write the formulae of the following complexes:
i. Pentamminechlorocobalt(III) ion
ii. Lithium tetrahydroaluminate(III) ion

Solutions to Exercise Questions:

1. c
2. c
3. A ligand may contain one or more unshared pair of electrons which are
called the donor sites of ligands. Now, depending on the number of these
donor sites, ligands can be classified as follows.
a. Unidentate ligands:
Ligands with only one donor site are called unidentate ligands.

b. Bidentate ligands:
 Ligands that have two donor sites are called bidentate ligands.

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

4.
a. [Co(H2O)(CN)(en)2]2+
Let the oxidation number of Co is be x
The charge on the complex is +2
[Co(H2O)(CN)(en)]+2
[x + 0 + (-1) + 2(0)] = +2
(x – 1) = +2
x = +3

b. [Pt(Cl)4]2-
Let the oxidation number of Pt be x
The charge on the complex is -2
[Pt(Cl)4]2-
[x + 4(-1)] = -2
(x – 4) = -2
x = +2

c. [Co(Br)2(en)2]2+
[x + 2(-1) + 2(0)] = +1
(x – 2) = +1
x = +3
d. K3[Fe(CN)6]
i.e., [Fe(CN)6]3-
[x + 6(-1)] = -3
(x – 6) = -3
x = -3 + 6
x = +3

e. [Cr(NH3)3Cl3]
[x + 3(0) + 3(-1)] = 0
(x – 3) = 0
x = +3
5.
a. Pentammine nitrito cobalt (II) chloride
b. Potassium hexacyano chromate (III)
6.
a. [Co(NH3)5Cl]
b. Li[AlH4]
7.

IUPAC name of A = pentaaquathiocyanatoferrate (III) ion

B = Hexafluoroferrate (III)
8.
I. Pentamminenitritocobalt (III) chloride
II. Potassium hexacyanochromate (III)
III. Pentamminecarbonatochromium (III) chloride.

9.
29Cu = 1s2 , 2s2 2p6, 3s2 3p6 3d10, 4s1
2 2 6 2 6 10 2
30Zn = 1s , 2s 2p , 3s 3p 3d , 4s
 On the basis of configuration of Cu and Zn, first ionization potential of Zn is
greater than that of copper because in zinc the electron is removed from
4s2 configuration while in copper it is removed from 4s1 configuration. So
more amount of energy is required for the removal of electron of 4s2
(completely filled orbital) than that of 4s1 while the second ionization
potential of Cu is higher than that of zinc because Cu+ has 3d10 (stable
configuration) in comparison to Zn+ (4s1 configuration).
10. Pentammine isothiocyanato chromium (III) tetra chlorozincate.

This compound is coloured because Cr3+ has 3d3 configuration (has unpaired
electron in d – orbitals) which show colour, through d - d transition.

11.
i. Formula of pentamminechlorocobalt (III) is [CoCl(NH3)5]2+.
ii. Formula of lithium tetrahydroaluminate (III) is LiAlH4
 Co-ordination Compounds
Module 24.2: Theories of Co-ordination compounds
To explain the formation of complex compounds many theories have been
suggested. The most successful of the earliest theories is Werner’s theory. It is
based on certain assumptions which are listed here.
Werner’s Theory of Co-ordination compounds:
Postulates
1. A complex has always a central metal atom. This may be an ion or a neutral
atom.
2. A metal in a complex compounds has two types of valencies, namely
primary and secondary valencies.
3. Primary valency (Ionisable valency) corresponds to the oxidation state of
metal atom or ion. Secondary valency (Non-ionisable valency) corresponds
to the co-ordination number of the central metal.
4. Every metal has a fixed number of secondary valencies or co-ordination
number in each of its oxidation states.
5. The co-ordination number of the metal is the number of ligands, which
gives the number of coordinate covalent bonds formed with central metal
atom or ion, in a complex compound.
In majority of the commonly found complex compounds, the co-ordination
number 2 or 4 or 6.
i) Co(III) and Pt(IV) have 6 co-ordination number
Ex: [Co(NH3)6]Cl3 ; K2[Pt(Cl)6]
ii) Cu(II), Pt(II), Zn(II) have 4 Co-ordination number
Ex: [Cu(NH3)4]2+ ; [Cu(OH)4]2- ; [Pt(NH3)4]+2 ; [Zn(CN)4]-2 ; [ZnCl4]-2
iii) Ag(I) has 2 Co-ordination number
Ex: [Ag(NH3)2]+ ; [Ag(CN)2]-
6. The secondary valencies of the central metal may be satisfied by negative
ions (Cl–, Br–, CN– etc..) or by neutral molecules (H2O, NH3 etc), or by
positive ions (NH2-NH3+, NO+ etc)
 In some complex compounds both primary and secondary valencies may be
satisfied by negative ions.
Ex: [Co(NH3)4Cl2]Cl
7. The primary valency can be satisfied by negative ions.
8. The ligands are directed in space around the central atom symmetrically in
such a way that the complex has a definite structure.
Ex: i) If the complex has 2 ligands, it gives linear structure.
[Ag(NH3)2]+; [H3N – Ag – NH3]+
ii) If the complex has 4 ligands, it assumes either a tetrahedral or a square
planar structure.
Ex:

iii) If the complex has 6 ligands it gives octahedral structure.

Ex: [Co(NH3)6]+3

9. The charge of complex ion is equal to the sum of charges of metal and
ligands.
Ex 1 : K4[Fe(CN)6]
 Oxidation state of Fe is +2
Oxidation state of CN– is –1
Charge of complex ion [2+6(-1)] = – 4
i.e., [Fe(CN)6]4–

Ex 2 : [Co(NH3)6]+3 [Cl–]3
Oxidation state of Co is +3
Oxidation state of NH3 is 0
Charge of complex ion (+3) + 6(0) = +3
i.e., [Co(NH3)6]3+

Advantages of Werner’s theory:

a) Werner’s theory can explain the isomerism in complex compounds.
Ex: [Co(NH3)4(NO2)2]+ give two isomers

b) We can distinguish the following complex compounds of same molecular

formula
[Co(NH3)5SO4]Br [Co(NH3)5Br]SO4
(I) (II)
[Co(NH3)5SO4]Br gives yellow precipitate with AgNO3.
[Co(NH3)5Br]SO4 gives white precipitate wit BaCl2 solution.
Defects in Werner’s theory:
Inspite of the capacity to explain the formation of complex compounds, Werner’s
theory is having many defects. Some of the important drawbacks are enumerated
here.
1. Werner’s theory does not correlate electronic configuration of the central
metal with the formation of the complex compounds. Now it is known that the
central metal try to acquire the next inert gas structure through coordinate
bond formation. Hence complexes are formed.
2. The postulates of Werner do not offer any explanation to the colour of the
complex compounds. It is appropriate at this juncture, to know how the d – d
transition takes place and result in the colour to the complex.
3. Werner’s theory is incapable of explaining the magnetic behavior. The
magnetic property depends on the number of unpaired electrons present in
the metal ion. Werner’s theory is not related to electronic configuration and so
this property could not be explained.

Sidgwick Theory of Co-ordination compounds:

Sidgwick suggested that the bond between the ligands and the metal ion is
co-ordinate covalent or semipolar bond. He says that the ligands donate the
electron pair to metal ion forming a coordinate covalent bond. Here ligand (L) is
donor and metal ion (M) is acceptor.
It is denoted by “L → M”
According to Sidgwick’s concept, the structure of the complex ion [Co(NH3)6]3+ is
represented as

Here, each NH3 donates a lone pair of electrons to cobalt (III) ion. The donation is
represented by an arrow. In the process the central atom acquires the same or
nearest number of electrons as that of its nearest inert gas. This number is known
as EAN. The principle is referred commonly as EAN rule.

Effective atomic number (EAN):

“The total number of electrons the central metal ion possesses including those
gained from ligands in the bonding, is called Effective Atomic Number (EAN)”
In many complexes it is equal to the atomic number of the nearest inert gas.
EAN value of metal can be calculated as follows using the relation.
EAN = {(Atomic number of metal) – (Oxidation state of metal) + [2×number of ligands]}
Many complexes obey EAN rule

At. no. No. of e’s At. No.

Complex Central No. of e’s EAN of the
S.No of the lost = Ox. of next
compound metal gained (y) metal = (z-x+y)
metal State(x) inert gas

1. [Co(NH3)6]Cl3 Co 27 3 12 (27-3+12)=36 36(Ar)

2. K4[Fe(CN)6] Fe 26 2 12 (26-2+12)=36 36(Ar)
3. [Pd(NH3)6]SO4 Pd 46 4 12 (46-4+12)=54 54(Xe)
4. [PtCl6]–2 Pt 78 4 12 (78-4+12)=86 86(Rn)

Some complexes do not obey EAN rule

Ex: 1) [Fe(CN)6]3– (26-3+12) = 35
2) [Ni(CN4)]2– (28-2+8) = 34

Valence Bond Theory:

This theory was developed by Pauling. This can explain the kind of bonding, shape
and magnetic properties of complex compounds. Main points are…
1. The central metal atom or ion makes available the necessary number of
vacant orbitals to suit its co-ordination number. These orbitals are
hybridized together, depending on the structure and shape hybrid orbitals.
2. The ligands must have at least one lone pair of electrons.
3. The vacant metal orbitals and lone pairs of electrons of the ligand orbitals
overlap to form coordinate covalent bonds.
4. The non-bonding metal electrons occupy the inner d-orbital which do not
involve in the hybridization.
5. If a complex contains unpaired electrons, it is paramagnetic in nature; if it
does not contain unpaired electrons it is diamagnetic in nature.
6. The number of unpaired electrons in complex may indicate the geometry of
the complex.
7. From the number of unpaired electrons in the complex the extent of
paramagnetism can be calculated.
8. The central metal atom may utilize the d-orbitals of either the penultimate
shell or the valence shell resulting in the inner d-orbital complexes or outer
d-orbital complexes respectively.
9. Sometimes the electrons undergo rearrangement against the Hund’s max
multiplicity rule.
 Geometry (shape) and magnetic nature of some complexes (application of Valence bond Theory)

Configuration No. of
Ox. Hybridi Geometry
Complex Unpaired Magnetic nature
state zation shape
electrons
[NiCl4]2– : ::: +2 sp3 Tetrahedral 2 Paramagnetic

sp3

[Ni(CN)4]– : : : : +2 dsp2 Square 0 Diamagnetic

planar
dsp2

[Fe(CN)6]4– :: : ::: +2 d2sp3 Octahedral 0 Diamagnetic

d2sp3

[Co(H2O)6]+2 : ::: :: +2 sp3d2 Octahedral 3 Paramagnetic

sp3 d2
Examples of inner orbital complexes and outer orbital complexes:
Ex 1: Formation of [Fe(CN)6]4– : The electronic configuration of Fe and Fe+2 ion in
Ferrocyanide ion is given below

In presence of cyanide ligand, the electrons in the 3d orbitals are forced to pair
up. Here Fe+2 undergoes d2sp3 hybridisation to form six d2sp3 hybrid orbitals, each
of them accepts electron pair donated by cyanide ion

Another inner orbital complex is [Co(NH3)6]3+

Outer orbital complex:

Ex-1: Formation of [CoF6]3–: The electronic configuration of Co+3 ion is given
below (outer orbitals configuration is 3d6 4s0)
The fluoride ion is a weak ligand and cannot force the pairing up of electrons.

Drawbacks of Valence Bond Theory:

1. It is a qualitative approach describing bonding in co-ordination compounds.
2. The theory fails to explain the finer aspects of the magnetic properties of
co-ordination compounds.
3. This theory does not provide an answer to the origin of characteristic
colours of complex ions.
4. It does not explain why [Co(NH3)6]+3 is an inner orbital complex and
[CoF6]-3 is an outer orbital complex.

Assignment Questions:
(1) Write the postulates of Werner’s theory.
(2) Explain Werner’s theory giving one example.
(3) Write the postulates of Valence Bond Theory.
(4) Explain the formation of [Fe(CN)6]4- and [CoF6]–3 on the basis of VBT (Z of Fe
= 26; Z of Co = 27).
(5) Define EAN.

Example Set:
1. EAN of Fe in [Fe(CN)6]3– is
a) 36 b) 27 c) 38 d) 35
Solution: d
2. The hybridisation undergone by Ni in [Ni (CN)4]2– ion is
a) dsp2 b) sp2d2 c) d2sp d) sp2
Solution: a

3. Which of the following has a central metal atom that has undergone d 2sp3
hybridisation?
 a) [Cr(NH3)6]2+ b) [Fe(CN)6]3–
c) [Co(NH3)6]3+ d) all are correct
Solution: d
4. According to Werner’s Theory the primary valency of the transition metal
ion is equal to
a) Oxidation state
b) Co-ordination number
c) Number of electrons in the outer most orbit
d) Atomic number
Solution: a
5. Write the formula to calculate the EAN of a central metal atom / ion.
Solution: EAN = {(Atomic number of metal) – (Oxidation state of metal) +
[2×number of ligands]}
6. What type of hybridisation undergone by Co in the complex [Co(NH3)6]3+?
Solution: d2sp3 hybridisation
7. Write a short not on i) Primary valency ii) Secondary valency of a metal in a
complex.
Solution:
i) Primary valency (Ionisable valency) corresponds to the oxidation state of
metal atom or ion.
ii) Secondary valency (Non-ionisable valency) corresponds to the Co-
ordination number of the central metal.
8. What are the possible shapes of complex ion with Co-ordination number 4
and 6?
Solution: Tetrahedral and square planar.

Problem Set:
1. According to Werner’s Theory the number of secondary valencies of a
transition metal ion is equal to the
a) Oxidation state
b) Atomic number
c) Co-ordination number
d) Unpaired electrons
 Solution: c
2. Which compound is formed when excess of KCN is added to aqueous
solution of copper sulphate?
a. Cu(CN)2
b. K2[Cu(CN)4]
c. K[Cu(CN)2]
d. K3[Cu (CN)4]
Solution: d
3. In the process of extraction of gold,
O2
Roasted gold ore + CN− + H2O ⎯⎯⎯ → [X] + O−
[X] + Zn → [Y] + Au
Identify the complexes [X] and [Y]
a. X = [Au(CN)2]− , Y = [Zn (CN)4]2-
b. X = [Au(CN)4] 3− , Y = [Zn (CN)4]2-
c. X = [Au(CN)2] − , Y = [Zn (CN)6]4-
d. X = [Au(CN)4] − , Y = [Zn (CN)4]2-
Solution: a
4. The EAN of nickel in K2[Ni(CN)4] is
a) 35 b) 34 c) 36 d) 38
Solution: b
5. Which of the following pairs contain only tetrahedral complexes?
a) [Ni(CN)4]2- and [CuCl4]2-
b) [Ni (CO)4] and [ZnCl4]2-
c) [Ni(NH3)4] and [Cu(NH3)4]2-
d) [Ni(NH3)4] and [Ni(CO)4]2-
Solution: b
6. The hybridisation state of the Fe among [Fe (CN)6]3- , Fe(CO)5, [Fe(H2O)6]2+
a) sp3d2, dsp3, sp3d2
b) d2sp3, dsp3, sp3d2
c) d2sp3, sp3d, sp3d2
d) sp3d2, sp3d, d2sp3
Solution: b
 7. Explain the terms inner orbital complex and outer orbital complex.
Solution:
Examples of inner orbital complexes and outer orbital complexes:
Ex 1: Formation of [Fe(CN)6]4– : The electronic configuration of Fe and Fe+2 ion in
Ferrocyanide ion is given below

In presence of cyanide ligand, the electrons in the 3d orbitals are forced to pair
up. Here Fe+2 undergoes d2sp3 hybridisation to form six d2sp3 hybrid orbitals, each
of them accepts electron pair donated by cyanide ion

Another inner orbital complex is [Co(NH3)6]3+

Outer orbital complex:
Ex-1: Formation of [CoF6]3–: The electronic configuration of Co+3 ion is given
below (outer orbitals configuration is 3d6 4s0)

The fluoride ion is a weak ligand and cannot force the pairing up of electrons.
 8. Calculate the EAN of the following metals in the following complexes
a) [Co(NH3)6]3+ b) [Pd(NH3)6]SO4 c) [Fe(CN)6]4– d) [PtCl6]–2
Solution:
S.No Complex Central At. no. No. of No. of EAN of the At. No.
compound metal of the e’s lost = e’s metal = (z-x+y) of next
metal Ox. gained inert
State(x) (y) gas

1. [Co(NH3)6]Cl3 Co 27 3 12 (27-3+12)=36 36(Ar)

2. K4[Fe(CN)6] Fe 26 2 12 (26-2+12)=36 36(Ar)
3. [Pd(NH3)6]SO4 Pd 46 4 12 (46-4+12)=54 54(Xe)
4. [PtCl6]–2 Pt 78 4 12 (78-4+12)=86 86(Rn)

9. Discuss the nature of bonding in the following co-ordination entities on the

basis of valence bond theory.
i) [Fe(CN)6]4– ii) [FeF6]3–
Solution:
i) [Fe(CN)6]4–
In the above co-ordination complex, iron exists in the +II oxidation state.
Electronic configuration of Fe+2 is 3d6 4s0.
Orbitals of Fe+2 ion:

As CN– is a strong ligand, it causes pairing of the unpaired 3d electrons.

Since there are six ligands around the central metal ion, the most feasible
hybridisation is d2sp3.
d2sp3 hybridized orbitals of Fe+2 are

6 electron pairs form CN– ions occupy the six hybrid d2sp3 orbitals
Then,

Hence, the geometry of the complex is octahedral and the complex is

diamagnetic (as there are no unpaired electrons)
ii) [FeF6]3–
In this complex, the oxidation state of Fe is +3.
Orbitals of Fe+3 ion are

There are 6F– ions. Thus, it will undergo d2sp3 or sp3d2 hybridisation. As F– is
a weak ligand, it does not cause the pairing of the electrons in the 3d
orbital. Hence, the most feasible hybridisation is sp3d2.
 Hence, the geometry of the complex is found to be octahedral.

Exercise Questions:

1. Amongst Ni(CO)4 , [Ni(CN)4]2- and NiCl2-

4
a. Ni(CO)4 and NiCl2- 2-
4 diamagnetic and [Ni(CN)4] is paramagnetic.
b. NiCl2- 2-
4 and [Ni(CN)4] are diamagnetic and Ni(CO)4 is paramagnetic
c. Ni(CO)4 and [Ni(CN)4]2- are diamagnetic and NiCl2-
4 is paramagnetic
d. Ni(CO)4 is diamagnetic and NiCl2- 2-
4 and [Ni(CN)4] are paramagnetic
Answer: c
2. Among the following, the compound that is both paramagnetic and colored
is
a. K2Cr2O7
b. (NH4)2(TiCl6)
c. CoSO4
d. K3[Cu(CN)4]
Answer: c

3. The geometry of Ni(CO)4 and [Ni(PPh3)2]Cl are

a. Both square planar
 b. Tetrahedral and square planar, respectively
c. Both tetrahedral
d. Square planar and tetrahedral, respectively:
Answer: c
4. The complex ion which has no ‘d’ electrons in the central metal atom is
a. [MnO4]−
b.
[Co(NH3)6]3+
c. [Fe(CN)6]3−
d. [Cr(H2O)6]3+
Answer: a
5. The species having tetrahedral shape is ___
a. [PdCl4]2-
b. [Ni(CN)4]2-
c. [Pd(CN)4]2-
d. [NiCl4]2-
Answer: b
6. The spin magnetic moment of cobalt in the compound Hg[Co(SCN)4]is
a. 3
b. 8
c. 15
d. 24
Answer: c
7. Which kind of isomerism is exhibited by octahedral Co(NH3)4 Br2Cl
a. Geometrical and ionization
b. Geometrical and optical
c. Optical and ionization
d. Geometrical only
Answer: a
8. Among the following metal carbonyls, the C – O bond order is lowest in
a. [Mn(CO)6]+
b. [Fe(CO)5]
c. [Cr(CO)6]
 d. [V(CO)6]-
Answer: d
9. Among the following the colored compound is
a. CuCl
b. K3[Cu(CN)4]
c. CuF2
d. [Cu(CH3CN)4]BF4
Answer: c
10.Both [Ni (CO)4] and [Ni(CN)4]2- are diamagnetic. The hybridization of nickel
in these complexes, respectively are
a. sp3, sp3
b. sp3,dsp2
c. dsp2, sp3
d. dsp2 , sp2
Answer: b
11.The spin only magnetic moment value (in Bohr magneton units) of Cr(CO)6
is
a. 0
b. 2.84
c. 4.90
d. 5.92
Answer: a
12. The complex showing a spin – only magnetic moment of 2.82 B.M. is
a. Ni(CO)4
b. [NiCl4]2-
c. Ni(PPh3)4
d. [Ni(CN)4]2-
Answer: b

13.[Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain why?

Solution:
Cr is in the +3 oxidation state i.e. d3 configuration. Also, NH3 is a weak field
ligand that does not cause the pairing of the electrons in the 3d orbital.
 Therefore it undergoes d2sp3 hybridisation and the electrons in the 3d
orbitals remain unpaired. Hence it is paramagnetic in nature.
In [Ni(CN)4]2– , Ni exists in the +2 oxidation state i.e., it has d84s0
configuration.

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.

14.[Ni(CO)4] possesses tetrahedral geometry while [Ni(CN)4]2– is a square

planar. Explain why?
Solution:
In the formation of Ni(CO)4 nickel is in zero oxidation state. It undergoes sp3
hybridisation; hence it is tetrahedral in shape.
 In the formation of [Ni(CN)4]2–, Ni2+ ion undergoes dsp2 hybridisation,
hence it is square planar in shape.

15.Explain, why 𝑁𝐻4+ ion does not form complexes?

Solution:
𝑁𝐻4+ Ion does not act as ligand because nitrogen atom has no lone pair of
electrons which it can donate to metal atom.

16.Calculate the magnetic moment of Mn in [MnCl4]2–.

Solution:
In [MnCl4]2– ion, Mn+2 ion undergoes sp3 hybridisation. It contains 5d-
orbitals singly occupied. Hence, it has high value of magnetic moment.
 Number of unpaired electrons = 5
∴ 𝜇 = √𝑛(𝑛 + 2)
= √5(5 + 2) = √35 = 5.92 BM

17.Explain why octahedral complexes of Ni2+ must be outer orbital complexes.

Solution:

During rearrangement only one 3d-orbital may be made available by

pairing the electrons. Thus, inner d2sp3 hybridisation is not possible. So,
only sp3d2 (outer) hybridisation can occur.

18.Identify the complexes which are expected to be colored. Explain

i. [Ti(NO3)4] ii. [Cu(NCCH3)4]+ BF4- iii. [Cr (NH3)6]3+ 3Cl- iv. K3[VF6]
Solution:
i. [Ti(NO3)4]; 22Ti4+ : [Ar]3d0 4s0
ii. [Cu(NCCH3)4]+ BF4- ; 29Cu+ : [Ar]3d10 4s0
iii.[Cr (NH3)6]3+ 3Cl- ; 24 Cr3+ : [Ar]3d3 4s0
iv. K3[VF6]; 23V+3 : [Ar]3d2 4s0

19.Draw the structures of Co(NH3)6]3+, [Ni(CN)4]2- and [Ni(CO)4. Write the

hybridization of atomic orbitals of the transition metal in each case.
Solution:
3d 4s 4p
Co3+

 d2sp3

NH3 3+

NH3 NH3
Octahedral
Co

NH3 NH3
NH3

[Ni(CN)4]2-
3d 4s 4p
2+
Ni
Ni2+ (after rearrangement)

dsp2
Pairing due
to CN-

CN CN 2-
Square planar
Ni

CN CN

[Ni(CO)4]
3d 4s 4p
Ni =
Ni (after rearrangement)

Pairing due to
sp3
CO
 CO

Ni

CO CO
CO

Tetrahedral

20. A metal complex having composition Cr(NH3)4Cl2Br has been isolated in

two forms (A) and (B). The form (A) reacts with AgNO3 to give a white
precipitate readily soluble in dilute aqueous ammonia, whereas (B) gives a
pale yellow precipitate soluble in concentrated ammonia. Write the
formula of (A) and (B) and state the hybridization of chromium in each.
Calculate their magnetic moments (spin only values).
Solution:
Compound (A) on treatment with AgNO3 gives white precipitate of AgCl,
which is readily soluble in dil.aq.NH3. Therefore it has at least one Cl- ion in
the ionization sphere furthermore chromium has co-ordination number
equal to 6. So its formula is [Cr(NH3)4BrCl]Cl.

Compound (B) on treatment with AgNO3 give pale yellow precipitate of

AgBr soluble in conc.NH3. Therefore it has Br- in the ionization sphere. So its
formula is [Cr(NH3)4Cl2] Br.
Cr3+ (Z = 24) has 3d3 configuration
Hybridization of chromium in both (A) and (B) is d2sp3.
Spin magnetic moment of (A) or (B),
spin = n(n+2) = 3(3+2) =3.87BM

21.Deduce the structure of [NiCl4]2-and [Ni(CN4)]2- considering the

hybridization of the metal ion. Calculate the magnetic moment (spin only)
of the species.
Solution:
 Cl- is a weak ligand which is unable to pair the electrons of Ni2+,
Hybridisation is sp3 and shape will be tetrahedral, with 2 unpaired
electrons.
Electronic configuration of Ni2+ in presence of Cl- ion, a weak ligand.
Magnetic moment = 2(2+2) = 2.82 BM
On the other hand CN- is a strong ligand which pairs up the electrons of
Ni2+. Therefore, here hybridization is dsp2 and shape will be square planar,
with unpaired electrons. u = 0
22.Write the IUPAC nomenclature of the given complex along with its
hybridization and structure
K2[Cr(NO)(NH3)(CN)4], µ = 1.73 BM
Solution:
The spin magnetic moment, µ of the complex in 1.73 BM.
µ = n(n+2) = 1.73  n = 1
It means that nucleus of the complex; chromium ion has one unpaired
electron. So the ligand NO is unit positively charged.
IUPAC name:
Potassium amminetetracyanonitrosochromate(I).
(a) Electronic configuration of Cr+:
3d 4s 4p

(b) Electronic configuration of Cr+ under the influence of strong field ligand
CN-

3d 4s 4p
Cr+

d2sp3
So, hybridization is d2sp3 and shape is octahedral
 Co-ordination Compounds
Module 24.3: Isomerism
Two or more molecules having the same molecular formula but different
structural or spatial arrangement are called isomers.
They are of two types.

a. Structural isomerism
b. Stereo isomerism

Stereo isomerism in complex compounds:

Two or more complexes having same molecular composition but different

arrangement of atoms (or) groups in space is called as stereoisomerism.

It is of two types.

a. Geometrical isomerism
b. Optical isomerism

Geometrical isomerism in co-ordination number 6 compounds:

The arrangement of six ligands in a complex around the central metal ion is
possible in two different ways. Those are regular hexagon and regular
octahedron.
If the complex Ma4b2 (where M = central metal atom; a,b = ligands) has hexagonal
structure it can give three isomers corresponding to (1, 2), (1, 3) and (1, 4)
positions of a and b, while octahedral arrangement can give only two isomers. X –
ray analysis confirmed that co-ordination number 6 complexes exhibit octahedral
arrangement by giving two isomers of Ma4b2 type. Hence co-ordination number 6
complexes have octahedral structure.

1. No isomerism is possible in [Ma6] or Ma5b of complexes

Example: [Co(NH3)6]3+; [Co(NH3)5Cl]2+

2. [Ma4b2] and [Ma4bc] type of complexes can give two isomers. Those are cis
and trans – isomers.

Example: [Co(NH3)4Cl2]+ gives cis and trans isomers.

3. [Ma3b3] type of complexes can exhibit geometrical isomerism.

Example: [Co(NH3)3Cl3] gives Cis – trans isomers.

4. [M(aa)2b2] (where aa = bidentate ligand) type of complexes having two
bidentate ligands, can exhibit geometrical isomerism.

Example: [Co(en)2Cl2]+ gives cis and trans isomers.

Optical isomerism in co-ordination number 6 compounds::

1. The cis isomer of [M(aa)2b2] type complexes has no plane of symmetry. So it

can give two isomers (d and l)

2. Complexes of [M(aa)3] type having three bidentate ligands are also

unsymmetrical and gives optical isomerism.

Example: [Pt(en)3]4+ gives optical isomers.

Stereo isomerism in co-ordination numbers 4 compounds:

Complex compounds with co-ordination number 4 give either tetrahedral or

square planar structure.

1. No isomers are possible [Ma4], [Ma3b] types complexes (square planar or

tetrahedral)

Example: Ni(CO)4, [Cu(NH3)4]2+

2. [Ma2b2] and [Ma2bc] complexes of some metals like Pt (II), Pd (II), Ni (II), Cu (II)
give square planar structure having dsp2 hybridization.

Example: [Pt(NH3)2(CN)2] gives cis, trans isomers

The geometrical isomers of [Pt(NH3)2Cl2] are

Some complex compounds of Cu, Zn, Ni can give tetrahedral structure. These
metals undergo sp3 hybridisation

[Mabcd] type of complex gives optical isomerism, if it has tetrahedral structure.

Three geometrical isomers are possible, if they have square planar structures.

Example: [Pt(NH3)(Py)ClBr] gives three isomers.

Assignment Questions:

1. Draw the structures of optical isomers of

a. [Pt(en)3]4+
b. [Co(en)2Cl2]+

Example Set:

1. Which one of the following square planar complexes will show cis – trans
isomerism
 a. Ma4
b. Ma3b
c. Ma2b2
d. Mabcd

Solution: c)

2. The number of isomers possible for square planar complex K2[PdClBr2(SCN)]

a. 2
b. 4
c. 5
d. 6

Solution: a)

3. Write an account on geometrical isomerism in complexes giving examples.

Solution:

Geometrical isomerism in co-ordination number 6 compounds:

The arrangement of six ligands in a complex around central metal ion is possible
in two different ways. Those are regular hexagon and regular octahedron.

If the complex Ma4b2 (where M = central metal atom; a = ligand) has hexagonal
structure it can give three isomers corresponding to (1, 2), (1, 3) and (1, 4)
positions of a and b, while octahedral arrangement can give only two isomers. X –
ray analysis confirmed that co-ordination number 6 complexes exhibit octahedral
arrangement by giving two isomers of Ma4b2 type. Hence co-ordination number 6
complexes have octahedral structure.
1. No isomerism is possible in [Ma6] or Ma5b of complexes

Example: [Co(NH3)6]3+; [Co(NH3)5Cl]2+

2. [Ma4b2] and [Ma4bc] type complexes can give two isomers. Those are cis and
trans – isomers.

Example: [Co(NH3)4Cl2]+ gives cis and trans isomers.

3. [Ma3b3] type of complexes can exhibit geometrical isomerism.

Example: [Co(NH3)3Cl3] gives cis – trans isomers.

Problem Set:

1. Geometrical isomerism would be expected from?

a. [Zn(NH3)2(H2O)2]2+
b. [Cu(CN)4]3-
c. [Pt(NH3)2Cl2]
d. [Ag(NH3)2]+
Solution: c)

2. Which of the following octahedral complexes does not show geometrical

isomerism (a and b are monodentate ligands)?
a. Ma3b3
b. Ma4b2
c. Ma5b
d. Ma2b4

Solution: c)

3. Draw structures of the geometrical isomers of [Fe(NH3)2(CN)4].

Solution:

Exercise Questions:

1. Why is geometrical isomerism not possible in tetrahedral complexes having

two different types of unidentate ligands?
2. Give evidence that [Co(NH3)5Cl)SO4 and [Co(NH3)5SO4]Cl are ionization
isomers?
3. Platinum (II) forms square planar complexes and platinum (IV) forms
octahedral complexes. How many geometrical isomers are possible for each of
the following complexes? Draw their structures.
a. [Pt(NH3)3Cl]+
b. [Pt(NH3)Cl5]-
c. [Pt(NH3)2Cl(NO2)]
d. [Pt(NH3)4ClBr]+2
Solutions to Exercise Questions:

1. b
2. Tetrahedral complexes do not show geometrical isomerism because the relative
positions of the unidentate ligands attached to the central metal atom are the
same w.r.t each other.

3.
a. A pair of optical isomers

It can also show linkage isomerism

[Co(NH3)5(NO2)](NO3)2 and [Co(NH3)5(ONO)](NO3)2

It can also show ionization isomerism

[Co(NH3)5(NO2)](NO3)2 and [Co(NH3)5](NO3)](NO2)(NO3)

b. Geometrical (cis-, trans-) isomers of [Pt(NH3)(H2O)Cl2] can exist

4.
a. No isomers are possible for a square planar complex of the type Ma3b. It is
[Ma3b] type of a complex
b. No isomers are possible for an octahedral complex of the type Mab 5. This is
a complex of the type Ma5b or Mab5

c. cis and trans isomers are possible for a square planar complex of the type
Ma2bc

d. cis and trans isomers are possible for an octahedral complex of the type
Ma4bc
5. A, B and C are three complexes of chromium (III) with the empirical formula
H12O6Cl3Cr. All the three complexes have water and chloride ion as ligands.
Complex A does not react with concentrated H2SO4, whereas complexes B and
C lose 6.75% and 13.5% of their original mass, respectively , on treatment with
concentrated H2SO4 identify A , B and C.

Solution:

The compound A does not react with concentrated H2SO4 implying that all water
molecules are coordinated with Cr3+ ion. Hence, its structure would be [Cr
(H2O)6]Cl3. The compound B loses 6.75% of its original mass when treated with
concentrated H2SO4. This loss is due to the removal of water molecules which
is/are not directly coordinated to Cr3+ ion.

The mass of water molecules removed per mole of the complex

6.75
= X molar mass of the complex
100
6.75
= X 266.5 g = 17.98 g (one mole H2O)
100
Compound B will be [Cr(H2O)5Cl](H2O)Cl2
The compound C loses 13.5 % of its mass when treated with concentrated
H2SO4 which is twice of the mass lost by the compound B. Hence compound
C will be [Cr (H2O)4Cl2] (H2O)2Cl.

7. The acidic, aqueous solution of ferrous ion forms a brown complex in the
presence of NO3- , by the following two steps. Complete and balance the
equations.
 [Fe (H2O)6]2+ + NO3- + H+ → …… + [Fe(H2O)6]3+ + H2O
[Fe(H2O)6]2+ + …… → ……+ H2O

Solution:

3[Fe (H2O)6]2+ + NO3- + 4H+ → NO + 3[Fe(H2O6)]3+ + 2H2O

[Fe (H2O)6]2+ + NO → [Fe(H2O)5 NO]2+ + H2O

8. Write the chemical reaction associated with the brown ring test.

Solution:

NaNO3 + H2SO4 → NaHSO4 + HNO3

6 FeSO4 + 2HNO3 + 3 H2SO4 → 3 Fe2(SO4)3 + 4 H2O + 2 NO
[Fe(H2O)6]SO4.H2O + NO → [Fe(H2O)5 NO] SO4 + 2 H2O
(brown ring)

9. Nickel chloride, when treated with dimethyl gyloxime in presence of

ammonium hydroxide, a bright red precipitate is obtained. Answer the
following.
a) Draw the structure of the complex showing H- bonds
b) Give oxidation state of nickel and its hybridization
c) Predict the magnetic behavior of the complex.

Solution:

(a)
O H–O

H3C – C = N N = C – CH3

Ni

H3C – C = N N = C – CH3

O–H O
 Bis(dimethylglyoximato) nickel (II).

(b) Charge on Ni in the complex is +2 and it is dsp2 hybridized.

(c) Since number of unpaired electrons in Ni2+ is zero, the complex is
diamagnetic.

SCN − F−
10. Fe3+ ⎯⎯⎯⎯
excess→ (A) ⎯⎯⎯⎯
excess → (B)
Blood red Colorless
Coloration

What are (A) and (B)? Give IUPAC Name of (A). Find the spin only
magnetic moment of (B).
Solution:
Fe3+ + SCN− → [Fe (SCN)(H2O)5]2+
(excess) (A)(blood red)

[Fe (SCN)(H2O)5]2+ + 6F− → [FeF6]3- + SCN-

IUPAC name of A is pentaaquathiocyanato ferrate (III) ion
IUPAC name of B is hexafluoroferrate (III)
In [FeF6]3- co-ordination no.of Fe = 6
In [FeF6]3- oxidation state of Fe = +3
 It has 3 unpaired electrons, n = 5
Magnetic moment = 35 = 5.92 B.M.

11.(Colourless liquid) MCl4 ⎯⎯⎯ Zn→ Purple color compound ; M = Transition

metal
MCl4 ⎯⎯⎯ Zn→ (B)
White fumes
Identify (A), (B) and MCl4. Explain color difference between MCl4 and (A).

Solution:

(A) [Ti(H2O)6]Cl3 (B) HCl

 Zn H2O
TiCl4 ⎯⎯⎯
heat→ TiCl3 ⎯⎯⎯ → [Ti(H2O)6]Cl3
Purple (A)

TiCl4 + (n + 2) H2O → TiO2 (H2O)n + 4 HCl ↑

White fumes
4+ 0 3+ 1
(B) Ti = [Ar] 3d ; Ti = [Ar]3d

TiCl4 is colorless since Ti4+ has no d electrons. Hence d-d transition is impossible.
On the other hand, Ti3+ is colored due to d-d transition. Ti3+ absorbs greenish
yellow compound of white light, hence its aqueous solution is purple which is
complementary color of greenish yellow in white light.

12. The number of water molecules (s) directly bonded to the metal centre in
CuSO4.5H2O is
Solution:
The number of water molecules directly bonding to the metal centre in
CuSO4.5H2O is 4

H2O
OH2
Cu2+ SO24− .H2O
H2O OH2

13.Total number of geometrical isomers for the complex

[RhCl(CO)(PPh3)(NH3)] is
Solution:
Four different ligands and hence three different arrangements.