CHEMISTRY

NMDCAT
Lecture # 9
(Transition Elements)
1. Introduction
2. Difference between d-block and f-block transition elements
3. Properties of Transition Elements
4. Electronic Configuraiton
5. General characteristics
a) Binding Energies b) Melting and Boiling Points
c) Covalent Radii and Ionic Radii d) Paramagnetism
e) Variable Oxidation State (OS) f) As a catalyst
g) Colour
h) Interstitiai Compounds i) Alloy Formation
6. Complex Compounds
• Components of Complex Compounds
a) Centeral Metal Ion b) Ligand
c) Coordination number d) Coordination Sphere
e) Charge on the coordination sphere
7. Nomenclature
8. Geometry of Complexes
 1. Introduction
Transition Elements
• Are those elements which have partially filled d or f sub-shell in
atomic state or in any of their commonly occurring oxidation
state
• Are those elements which lie in between s and p block elements
• May be defined as one which forms at least one ion with partially
filled d – sub shells (for d-block elements)
Typical transition elements of 3d-series: (Ti, V, Fe, Mn, Ni, Co)
Non–typical transition elements IIIB: (Sc, Y, La)
IIB: (Zn, Cd, Hg)
Group IIIB elements: They are transition elements by definition.
(have one electron in 3d sub-shell)
• But IIIB groups elements mostly occur as the tripositive ions (+3)
having no d-electron hence, they do not show the property of
transition elements (3d sub-shell vacant). In such condition they do
not form coloured compounds.
• IIB groups elements occur as the dipositive ions +2 (3d sub-shell
completely filled) and they do not form coloured compounds.
 2. Difference between d-block
and f-block elements
1. d-Block Elements
• The elements having partially filled d-subshell are called d-block
elements.
• Zinc, cadmium and mercury are also included in transition
elements although they have no partially filled d-orbital.
• Copper in zero state has no d-subshell partially filled but Cu2+
has configuration [Ar] 3s2, 3p6, 3d9 and transitional in character.
• Ag and Au also have no partially filled d-orbital in zero oxidation
state.
• But Ag2+ has 4d9 and Au3+ has 5d8 electronic configuration. d-
block elements are also called outer transition elements.
2. f-Block Elements
• “The elements having f-subshell partially filled in their common
oxidation state are called f-block elements, f-block elements are
also called inner transition elements”.
• f-block transition elements include two rows at the bottom of
periodic table.
• First row is called Lanthanides while second row is called
Actinides. All actinides are radioactive in nature.
 d – block elements f – block elements
Outer transition elements Inner transition elements
(Rare earth elements)
All the d-block elements are All the f-block elements are
classified into four series classified into two series
Periods Number of series Number of series
4 3d-series (21Sc – 30Zn) Lanthanide series
5 4d-series (39Y – 48Cd) (58Ce – 71Lu)
6 5d-series (57La – 80Hg) Actinide series
7 6d-series (90Th – 103Lr)
 9
3. Properties of Transition Elements

• Because of a similar electronic configuration, the d-block elements

closely resemble one another in their physical and chemical properties
• They show the following resemblance in their properties:
i. They are all metals in true sense (e.g. Ti, Fe, Cr, Ni, Cu etc.)
ii. They are all hard and strong metals with high melting and boiling points
iii. They are good conductor of heat and electricity (Cu, Ag, Au)
iv. They form alloys with one another and also with other elements
v. They show variable oxidation state (Fe+2, Fe+3)
vi. Their ions and compounds are coloured in solid state as well as in
solution form at least in one if not all the oxidation states (vii) catalysts
 Ar
Xe 3d
Kr 4f10
4d
5d158310
17
62514
412 212212210
5d 5364297 6s
4s
5s
4s
6s
5s
4s
5s 6s1212

10
4. Electronic Configuration
• General electronic configuration of d-block elements (n-1) d1-10 ns1-2

3d-block elements 4d-block elements 5d-block elements

Electronic Electronic Electronic
Elements Elements Elements
Configuration configuration configuration
Sc (21) [Ar]3d14s2 Y (39) [Kr]4d15s2 La (57) [Xe]5d16s2
Ti (22) [Ar]3d24s2 Zr (40) [Kr]4d25s2 Hf (72) [Xe]4f145d26s2
V (23) [Ar]3d34s2 Nb (41) [Kr]4d45s1 Ta (73) [Xe]4f145d36s2
Cr (24) [Ar]3d54s1 Mo (42) [Kr]4d55s1 W (74) [Xe]4f145d46s2
Mn (25) [Ar]3d54s2 Te (43) [Kr]4d55s2 Re (75) [Xe]4f145d56s2
Fe (26) [Ar]3d64s2 Ru (44) [Kr]4d75s1 Os (76) [Xe]4f145d66s2
Co (27) [Ar]3d74s2 Rh (45) [Kr]4d85s1 Ir (77) [Xe]4f145d76s1
Ni (28) [Ar]3d84s2 Pd (46) [Kr]4d10 Pt (78) [Xe]4f145d96s1
Cu (29) [Ar]3d104s1 Ag (47) [Kr]4d105s1 Au (79) [Xe]4f145d106s1
Zn (30) [Ar]3d104s2 Cd (48) [Kr]4d105s2 Hg (80) [Xe]4f145d106s2
Detailed Electronic Configuration of 11
Transition Elements of 3d-series
 12
Electronic Configuration of 3d-Series

• For 3d-series 3d1-10 4s1-2

• Electronic Configuration of 26Fe (Ar)

• Electronic Configuration of Fe2+

• Electronic Configuration of Fe3+

• Electronic configuration of Fe3+ is more stable than Fe2+ Because
Fe3+ has
half filled d sub-shell
 Q: Which of the following pair of elements show abnormal
electronic configuration?
A) Ni, Co C) Zn, Cu
B) Fe, Cr D) Cu, Cr
Explanation: (D) Cr and Cu show abnormal electronic configuration
24Cr (VIB) 29Cu (IB)

24Cr = (Ar) 29Cu = (Ar)

It has maximum no. of unpaired electron = 6 It has only one unpaired electron
Cr shows +3, +6 Oxidation States Cu shows +1, +2 Oxidation State
K2Cr2O7 orange red crystalline solid CuSO4.5H2O blue vitriol
 Electronic configuration of 30Zn Electronic configuration of Zn+2

(Ar) (Ar)
Characteristics Features of Zn
• Zn belongs to IIB group
• It is non-typical transition element
• It shows non-variable oxidation state (+2)
• It does not form coloured compounds
• It does not give Borex Bead Test
• It is used as reactive anode electrode in
a. Galvanic cell b. Dry alkaline cell c. Silver oxide cell
• ZnSO4.7H2O is known as white vitriol
Q: Electronic configuration of Manganese (25Mn) is:
A) (Ar) 3d5, 4s2 C) (Ar) 3d7, 4s2
B) (Ar) 3d10 4s1 D) (Ar) 3d8, 4s1
Explanation: (A) (Ar) 3d54s2.
Q: Electronic configuration of Gold [79Au] is:
A) [Xe] 4f14, 5d10, 6s1 C) [Xe] 4f14, 5d9, 6s2
B) [Xe] 4f10, 5d10, 6s2 D) [Xe ]4f14, 5d10, 6s2
Explanation: (A)
• [Xe] 4f14, 5d10, 6s1
• Au belongs to IB group
• Other elements of IB Cu, Ag
• The elements of IB group are known as coinage metals
Q: Which of the following pair of ions has maximum number of
unpaired electrons?
A) Mn+2, Fe+3 C) Mn+3, Fe+3
B) Ni+2, Zn+2 D) Cu+3, Co+2
Explanation: (A)
 Mn+2 (Ar) 3d5  Fe+3 (Ar) 3d5
Conclusion: From the electronic configuration of Mn+2 and Fe+3 it is
clear that both have maximum number of unpaired electrons (i.e. 5
unpaired electrons in 3d sub-shell).
Q: Which element of 3d series of periodic table shows the
electronic configuration of (Ar) 3d8, 4s2?
A) Copper C) Zinc
B) Cobalt D) Nickel
Explanation: (D) Ni element of 3d series of periodic table shows the
electronic configuration of 28Ni = (Ar) 3d84s2
 17

5. General Characteristics
a) Binding Energies
b) Melting and Boiling Points
c) Covalent Radii and Ionic Radii
d) Paramagnetism
e) Variable Oxidation State (OS)
f) As a catalyst
g) Colour
h) Interstitiai Compounds
i) Alloy Formation
 a) Binding Energies 18
• Transition metals show good mechanical properties. They are tough,
malleable and ductile. The toughness of these metals indicates strong
metallic binding. This is because, apart from s-electrons of the outer most
shell, the electrons of underlying half-filled d-orbitals also participate in
binding.
• In moving from left to right in any transition series, the number of unpaired
electrons increases up to group VB and VIB, after that pairing takes place
and number of unpaired electrons goes on decreasing until it becomes zero
at group IIB.
• Therefore binding is stronger up to group VIB and weakens progressively up
to group IIB. This trend of variation in binding energies is shown in figure. In
the first transition series, the general increase in binding energy ends at
vanadium. This is due to the change in metallic structure. Manganese has
somewhat low binding energy. In the third transition series, the increase in
binding energy ends at tungsten when all the 5d electrons contribute to
binding.
 b) Melting and Boiling Points 19
• Transition metals have very high melting and boiling points due to
strong binding forces present between their atoms.
• Melting points increase up to the middle of the series and then
decrease to a minimum level at the end of the series.
MCQ: Which one of the following transition elements of 3d-series has
highest melting point and boiling point?
A) Mn C) Zn
B) V D) Ti
Answer Explanation (B)
• In 3d-series the transition element ‘V’ has highest melting point and
boiling point.
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Melting point (oC) 1539 1668 1900 1875 1245 1536 1495 1453 1083 419.5
Boiling point (oC) 2730 3260 3450 2665 2150 3000 2900 2730 2395 906

• It is clear from the table that the melting points increases up to V

and then decreases. Similarly, the boiling point increases up to V and
then decreases.
 c) Covalent Radii and Ionic Radii 22
• The covalent radii decrease rapidly at
the start of the series, then become
almost constant, and finally begin to
increase at the end of the series.
• The increase in covalent radii is
possibly due to the fact that the filled
3d orbital have contracted into the
electron core and so shield the outer
4s electrons more effectively form the
nucleus.
• Changes in the ionic radii along the
series are much less regular, so that
periodic trends in the properties of
these ions are difficult to rationalize.
 MCQ: The covalent radii _________ rapidly at the start of the 3d
series and finally begins to _______ at the end of the series.
A) Increase, decrease C) Increase, increase
B) Decrease, Increase D) Decrease, decrease
Answer Explanation (B)
• Atomic radii of transition elernents in a period is smaller than s-block elernents and
larger than p-block elements.
• In a series, atomic radii decreases initially and varies irregularly showing near
consistency till 11th group and then in the 12th group.
• With increasing atomic number, nuclear charge and shielding effect of d-electrons
increase and counter balance the effects, resulting small decrease in atornic radii.
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic Radii (pm) 144 132 122 118 117 117 116 115 117 125
Ionic Radii (pm) 95 90 88 74 80 76 74 72 69 74
 d) Paramagnetism 24
Paramagnetic substances: Substances which are weakly attracted by a strong
magnetic field are called Paramagnetic substances. e.g. MnSO4, FeCl2, NiCl2 etc.
Diamagnetic substances: Those substances which are weakly repelled by a
strong magnetic field are called diamagnetic substances. e.g. ZnCl2, ScCl3, CuCl
etc.
 25

Q: Paramagnetic behavior of an atom, ion or molecule is due

to presence of:
A) Paired electrons C) Protons
B) Unpaired electrons D) Neutrons
Explanation: (B) Paramagnetic behavior of an atom, ion or molecule
is due to presence of unpaired electrons.
 26
e) Variable Oxidation State (OS)

Transition elements show variable oxidation state because electrons of

outer ns and inner (n-1) d participate in bonding
• Reason:
• Because energy difference between consecutive shells decreases as shown in the diagram
n=4 4p
• E2 – E1 > E3 – E2 > E4 – E3 E n=3
3d
4s
3p
3s
• So there is smaller energy difference between 4s and 3d subshell
• According to (n + l) rule electrons are preferentially filled first in 4s subshell than that of
3d subshell
• After filling of electrons, repulsion between electrons of 4s subshell and electrons of 3d subshell take place
because they are very close to each other. Thus energy of 4s subshell electrons increases That’s why during
ionization, electrons are first of all removed from 4s subshell than that of 3d subshell
 Points to be remembered
• Elements of 3d series shows +3 and +2 stable oxidation state (OS)
a. Elements in the beginning of series show stable +3 OS while elements at the end of
series shows +2 O.S
b. In lower oxidation state of +2 and +3 elements form ionic bonds e.g. CuSO4, FeCl3
c. All 3d series elements show an oxidation state of +2 in addition to higher O.S.
• Up to Mn (first five elements) transition elements show maximum O.S.
• Sc (+3), Ti (+4), V (+5), Cr (+6), Mn (+7)
a. Higher OS are found in the compounds of F and O e.g. KMnO4, K2Cr2O7
b. In higher OS, the elements form covalent bonds
• After that they show +2 O.S
Reason:
• After Mn, the increasing nuclear charge binds 3d-electrons more strongly and in such
condition only electrons of 4s sub-shell are easily removed during ionization. That is why the
elements show +2 oxidation state after Mn easily.
e.g. Fe (+2), Cu (+2), Ni (+2), Zn (+2)
 28
Q:
The common oxidation state of Ti are:
A) +2, +3 C) +3, -4
B) +3, +4 D) +2, +3, +4
Explanation: (D) The common oxidation state of Ti are +2, +3, +4.
22Ti

Electronic configuration Oxidation state

(Ar) 3d2 4s2 0
(Ar) 3d2 +2
(Ar) 3d1 +3
(Ar) 3d0 +4

Conclusion: It is clear that common oxidation state of Ti are +2, +3, +4.
Q: Which pair of compounds has same oxidation state of Fe:
A) FeSO4, FeCl3 C) Fe2(SO4)3, FeSO4
B) FeSO4, FeCl2 D) FeCl2, FeCl3
Explanation: (B) FeSO4, FeCl2 pair of compounds have same
oxidation state of Fe.

Q: Oxidation state of ‘Mn’ in KMnO4, K2MnO4, MnO2 and

MnSO4 is in the order respectively:
A) +7,+4,+2,+6 C) +7,+,6,+4,+2
B) +6,+7,+2,+4 D) +4,+6,+7,+2
Explanation: (C) Oxidation state of ‘Mn’ in KMnO4, K2MnO4, MnO2
and MnSO4 is in the order of +7,+6,+4,+2 respectively.
Q: The oxidation number of cobalt in K3[Co(NO2)6] is:
A) -3 C) -4
B) +3 D) +4
Explanation: (B) The oxidation number of cobalt in K3[Co(NO2)6] is +3.

Q: Study the following redox reaction:

𝟏𝟎𝐂𝐥− + 𝟏𝟔𝐇+ + 𝟐𝐌𝐧𝐎𝟒− → 𝟓𝐂𝐥𝟐 + 𝟐𝐌𝐧+𝟐 + 𝟖𝐇𝟐 𝐎
A) Manganese is oxidized from +7 to +2
B) Chlorine ions are reduced from -1 to zero
C) Chlorine is reduced from zero to -1
D) Manganese is reduced from +7 to +2
Explanation: (D) 𝟏𝟎𝐂𝐥− + 𝟏𝟔𝐇 + + 𝟐𝐌𝐧𝐎𝟒− → 𝟓𝐂𝐥𝟐 + 𝟐𝐌𝐧+𝟐 + 𝟖𝐇𝟐 𝐎
R.A O.A
Manganese is reduced from +7 to +2.
 31
f) As a catalyst
Transition elements are used as a catalyst
Reasons:
• Due to the presence of vacant d-orbitals
• Tendency to show variable O.S
• Tendency to form certain intermediate with reactants
How transition elements act as a catalyst?
Explanation:
a. The surface of a solid catalyst provides sites for the adsorption of
reacting molecules
b. Which causes weakening of certain bonds in the reacting molecules
c. And thus facilitates the reaction
 32

Transition Substance as a Reaction catalyzed

element catalyst
• TiCl4 + Al(C2H5)3
Ti (Ziegler-Natta)
Catalyst Polymerization of ethylene
V V2O5 In Contact tower SO2 + O2 ⇄ 2SO3 (Contact process for H2SO4)
Catalytic Hydrogenation of vegetable oil
Ni Ni
(Unsaturated) Vegetable Oil + H2  (Saturated) Vegetable Ghee
* Catalytic Oxidation of CH4,
Cu Cu

Pt Pt 4NH3 + 5O2  4NO + 6H2O (Ostwald’s method for HNO3)

 33

* It was discovered by two scientists, and I think we can all figure

out what their names were. Ziegler-Natta like TiCl3. We also know
that co-catalysts are involved, and these are usually based on
group III metals like aluminum. Most of the time our catalyst/co-
catalyst pair are TiCl3 and Al(C2H5)2Cl, or TiCl4 with Al(C2H5)3
 34
Q: Transition metals and their compounds are used as
catalysts. Which of the following statements is correct?
Transition metal acts as a Transition metal acts as a
Options
catalyst in Contact process catalyst in Haber’s process
A) Iron Iron
B) Iron Platinum
C) Platinum Iron
D) Platinum Platinum

Explanation: (C) Transition metal acts as Transition metal acts as

Options a catalyst in Contact a catalyst in Haber’s
process process
C) Platinum Iron
 g) Colour 35
Compounds of transition elements are usually coloured
• The colour of these complexes is due to the absorption of some
radiation from visible light which is used in causing intra d-d transition
In transition elements the d-orbitals (degenerate 3d-orbitals)
• Are responsible for the colour
development in their compounds
• When these orbitals are involved in bonding,
• (when the ligands approach)
• The d-orbitals split up into two energy levels
(i) One set of d-orbitals at lower energy level
(ii) Other set of d-orbitals at higher energy level
(iii) The electron residing in low energy d-orbitals absorb a part of
energy (the visible light) and jump to high energy d-orbitals
(iv) The process is called d-d transition
 36
Explanation: In [Ti(H2O)6]+3, yellow light is absorbed,
while most of the blue and red lights are transmitted,
therefore the solution of [Ti(H2O)6]+3 ions looks violet
in colour.
• [Ti(H2O)6]Cl3

• Violet in colour
d-d transition after
 absorption of ΔE

Ti H O  
+3

5d generate orbitals 2 6
Blue and red
+3
of Ti g  before absorbs yellow colour
 from visible light lights are transmitted
Ti H O  
approaching ligands +3
2
Excited state
6
Octahedral geometry
Ground state
 Transition metal complexes (coordination compounds) show
complementary colours i.e. one colour of characteristic
wavelength is absorbed. Then as a result in the excited state
colour of different characteristic wavelength is transmitted as
shown in the diagram.
Relationship between the colours of
the absorbed and transmitted light
Colour of the
Absorbed light Transmitted light
Yellow Violet
Orange Blue
Red Green
IR White
Q: Which one of the following pairs of ions is
colourless?
A) Ti3+, Cu2+ C) Co2+, Fe3+
B) Sc3+, Zn2+ D) Ni2+, V3+
Explanation: (B) Sc3+, Zn2+ is a pair of colourless ions.
Q: [Ti(H2O)6]+3 transmits: (2015)
A) Yellow and Red light C) Red and white light
B) Yellow and Blue light D) Red and blue light
Explanation: (D) [Ti(H2O)6]+3 transmits red and blue light.
 39
Q: Which of the following ions is colourless:
A) V+5 C) Ti+3
B) Cu+2 D) Fe+2
Explanation: (A) V+5 ions is a colourless. In this oxidation state V+5
ion does not formed coloured compound.
• For the formation of coloured compound transition metal cation
must have at least one unpaired electron in d subshell which is
very necessary for d-d transition
Q: Colour of transition metal ion is due to:
A) Small sized metal ions C) Complete ns subshell
B) Absorption of light in UV region D) d-d transition
Explanation: (D) d-d transition.
 40
h) Interstitiai Compounds
• When small non-metal atoms like H, B, N, C enter the
interstices of transition metals and impart useful features
to them, they are called interstitial compounds.
Examples: TiC, Mn4N, TiH, Fe3H etc.
(i) These are non-stoichiometric compounds.
(ii) They are neither typically ionic nor covalent.
(iii) They have some properties different from those
of transition metals.
e.g. hardness, melting points, chemical properties etc.
 i) Alloy formation 41
“A solid solution of metals is called alloy”. Due to the
similarity in their sizes, some transition metal atoms are able
to replace one another in the metallic lattice and form
substitutional alloys among themselves. Alloy steel is an
important example of this type of material in which iron atoms
are substituted by chromium, manganese and nickel atoms,
etc, to give the steel more useful properties. Other examples
are brass, bronze, coinage alloys, etc.
 42
6. Complex Compounds
Coordination compounds (Complexes compounds):
• Such compounds containing
Complex molecules or complex ions and
Capable of independent existence are
Called coordination compounds or complexes
• Types of Complexes
1. Simple cation and complex anion
e.g. K4[FeCN)6] Potassium hexacayno ferrate (II)
2. Complex cation and simple anion
e.g. [Cu(NH3)4]SO4 tetrammine copper (II) sulphate
3. Neutral Complexes
e.g. [Ni(CO)4] Tetracarbonyl nickel (0)
 43
Components of complex compound

Terms Definition
A metal atom or ion (usually a transition element)
a) Central Metal atom or Ion surrounded by a number of ligands is called a central metal
atom or ion, e.g. K4[*Fe(CN)6]
The atoms or ions or neutral molecules which surround the
central metal atom or ion and donate electron pairs to it, are
b) Ligand
called ligands. They may be anions or neutral molecules,
e.g. K4[Fe(*CN)6]
The number of lone pair of electrons provided by the ligands
c) Coordination number to the central metal atom or ion is called the coordination
number of the central metal atom or ion, e.g. K4[Fe(CN)*6]
The central metal atom or ion along with ligands is called the
d) Coordination sphere coordination sphere. It is usually placed in sphere brackets. It
may be anionic, cationic or neutral [Fe*(CN)6]
 44
Classfication of ligands
1. Monodentate, (or unidentate) ligands: The ligand
which can attack to the central metal/ion only through one
point, are termed monodentate ligands. They can donate one
lone pair of electron. Monodentate ligands may be neutral or
anionic, and are called by their specific names.
Neutral ligands Anionic
Formula Name Donour Atom Formula Name Donour Atom
H2O Aqua O F- Fluoro F
NH3 Ammine N Cl- Chloro Cl
CO Carbonyl C Br- Bromo Br
NO Nitrosyl N I- Iodo I
C5H5N Pyridine N H- Hydrido H
 45
2. bidentate ligands: The ligands which get attached to the
metal ion through two points are called bidentate ligands. i.e.
two lone pair of electrons. Some commonly used bidentate
ligands are given in the below.

Neutral Anionic
Donour Donour
Formula Name Formula Name
atom atom
CH 2  CH 2
Oxalato
Ethylenediamine (en) N C2O4-2 O
NH 2 NH 2 (OX)
 46
3. Tridentate ligands: Tridentate ligands have three lone
pairs of electrons to the central metal atom or ion.
e.g.
(i) Neutral Ligands

(ii) Charged Ligands (anionic ligands)

(iii) Phosphate ion PO43-
 47
4. Polydentate ligands The ligands having six sites of
attachment to the metal ion is (iv) hexadentate ligand i.e. it can
donate six lone pair of electrons.


CH 2  COO
-
OOC - H 2 C
 
N  CH2 2 N

OOC - H 2 C
CH 2  COO -

Ethylenediaminetetraaceto (EDTA)
The EDTA forms coordinate bonds with transition metal atom or ion
through four oxygen (O) atoms and two nitrogen (N) atoms.
Q: Consider the following structure of a coordination compound:

Which of the above letter denotes ligands?

A) Q C) X
B) Y D) Z
Answer Explanation: (C)
In the following given structure, the letter X indicates ligands.
Opt. Letters Nomenclature (Naming)
A) Q Central metal ion (Co3+)
B) Y Coordination number (2 + 4 =6)
C) X Ligands (Cl, NH3)
D) Z Ionisable anion
Q: Which one of the following is Tri-dentate ligands?
A) Acetate ion C) Oxalate ion
B) Phosphate ion D) Hydrazine
Answer Explanation: (B)
• Mono-dentate ligands:
i. Neutral ligands: (H2O, CO, NH3)
ii. Anionic ligands: (Cl, Br, I, CN, OH, CH3COO)
• Bi-dentate ligands:
i. Neutral ligands: (H2NNH2, H2NCH2CH2NH2)
ii. Anionic ligands: ( CO32 , SO 24 , C2O 42 )
• Tri-dentate ligands:
i. Neutral ligands: ( NH2   CH2 2  NH   CH2 2  NH2 )
Diethylene triamine (dien)
i. Anionic ligands: ( PO 34 )
Q: Coordination number and oxidation state of Cr in
K3[Cr(C2O4)3] are respectively:
A) 4 and +2 C) 6 and +3
B) 3 and +3 D) 3 and 0
Explanation: (C) Coordination number and oxidation state of Cr in
K3[Cr(C2O4)3] are respectively 6 and +3.
Q: Which one of the following is Tri-dentate ligands?
A) Acetate ion C) Oxalate ion
B) Phosphate ion D) Hydrazine
Answer Explanation: (C)
Coordination number and oxidation state of Cr in K3[Cr(C2O4)3] are
respectively 6 and +3.
Q: CO3-2 is a _________ ligand:
A) Tetradentate C) Hexadentate
B) Bidentate D) Tridentate
Explanation: (B) CO3-2 is a bidentate ligand. CO3-2 donates
two lone pairs of electrons to the transition metal ion.
 52
7. Nomenclature
The nomenclature of complex compounds is based upon the recommendations by the
Inorganic Nomenclature Committee of IUPAC.
The rules for naming the complexes are given below.
1. Cations are named before anions.
2. In naming the coordination sphere, ligands are named in alphabetical order
regardless of the nature and number of each, followed by the name of central metal
ion.
3. The prefixes di, tri, tetra, penta, hexa, etc, are used to specify the number of
coordinated ligands.
4. The names of anionic ligands end in suffix “O”, e.g, hydroxo, (OH–), carbonato (CO).
5. The names of neutral ligands are usually unchanged, e.g. for NH3, ammine, for H2O,
aqua and for CO, carbonyl.
6. The suffix ‘ate’ comes at the end of the name of metal if the complex represents an
anion, otherwise it remains unchanged.
7. The oxidation number of the metal ion is represented by a Roman numeral in
parenthesis following the name of the metal.
 53

Q: The correct formula of Tetrammineaquabromocobalt(III)

nitrate is:
A) [CoBr(NH3)4(H2O](NO3)2
B) [CoBr(H2O](NH3)4(NO3)2
C) [CoBr(NH3)4(H2O)Br](NO3)2
D) [Co(NO)(NH3)4(H2O)Br](NO3)2
Explanation: (A)
The correct formula of Tetrammineaquabromocobalt ( III) nitrate is
[CoBr(NH3)4(H2O](NO3)2.
 54
8. Geometry of Complexes
The geometry of complexes depend upon the type of orbital hybridization
taking place in the valence shell of the central metal atom or ion.

Type of Orbital
OS of T.E Examples
Geometry Hybridization
Linear sp Ag+1 [Ag(NH3)2]+1
Tetrahedral sp3 Mn+2, Zn+2, Ni (O) [MnCl4]-2, [Zn(CN)4]-2 Ni(CO)4
Square Planar dsp2 Cu+2 [Cu(NH3)]+2
Trigonal Pyramid dsp3 Fe(O) Fe(CO)5
[Co(NH3)6]+3 [Fe(CN)6]-4
Octahedral d2sp3 Fe2+, Fe3+, Cr+3, Pt+4
[PtCl2(NH3)4]+2
 Geometry of Complexes 55

[MnCl4]-2 [Cu(NH3)4]-2 [Fe(CO)5] [Co(NH3)6]-2

Cl CO NH3
H3N NH3 H3N NH3
CO
Mn
Fe CO Co
Cu
CO H3N NH 3
H3N NH 3
Cl Cl Cl CO NH3
Square planar Trigonal bipyramidal Octahedral
Tetrahedral (dsp2) (dsp3) (d2sp3)
(sp3)
Q: Transition metals commonly show which type of geometry:
A) Square planar C) Octahedral
B) Trigonal bipyramidal D) Linear
Explanation: (C) Transition metals commonly show octahedral
type of geometry.

Q: The geometry of the complexes depends upon the type of

________ taking place in the valence shell of the central metal
atom:
A) Protonation C) Deprotonating
B) Orbital hybridization D) Dissociation
Explanation: (B) The geometry of the complexes depends upon the
type of orbital hybridization taking place in the valence shell of the
central metal atom or ion.
 57
Q: In the complex of [Cu(CN)4]-3 the orbital hybridi zation,
oxidation state and number of unpaired electrons in copper
ion is:
A) dsp2, +1, 1 C) sp3, +1, zero
B) sp3, +2, 1 D) dsp2, +2, zero

Explanation: (C) In the complex of [Cu(CN)4]-3 the hybridization, oxidation

state and number of unpaired electrons in copper ion is sp3, +1, zero
respectively.
3d 4s 4p
Cu CN 4  = Ar      
-3
xx xx xx xx
sp3, +1, zero
CN CN CN CN
 • The given coordination compound is a type of a 58
simple cation and a complex anion.
Coordination Sphere

K 4  Fe CN  6 
Transition metal cation
Ligand
Coordination number
Q: The central atom or ion along with ligands is called:
A) Complex ion C) Coordination sphere
B) Ligand D) Complex compound
Explanation: (C) The central atom or ion along with ligands is called
coordination sphere.
Note:
FOR FURTHER MCQs SEE PRACTICE BOOK
WITH DETAILED EXPLANATION
Thank you!