➢ Addition Compounds or molecular compounds: -

When two or more salts are mixed in proper proportions and evaporate then,
crystals of compounds are formed. These crystals of compounds are called as
addition compounds or molecular compounds.
There are two types of addition compounds: -
❖ Double Salts
❖ Coordination Compounds

1) Double Salt: -
When Salt dissolved in water then, individual components shows their
individual property is called as double salt.
E.g., i) when carnallite [KCl.MgCl2.6H2O] dissolved in water then it gives,
the test for K+, Mg2+, Cl- ions.
ii) When potash alum [K2SO4.A12 (SO4)3 24H2O] dissolved in water then it
gives the test for K+, Al3+, SO42- ions.
iii) When Mohr's salt [Fe (SO4)2 (NH4)2.6 H2O] dissolved in water then it
gives test for Fe2+, NH4+, SO42- ions.

2) Coordination Compounds or Complex Compounds: -

When the compound dissolved in water then individual components does
not shows their individual property is called as coordination compound or
complex.
i) when complex ion [Co (NH3)6]3+ is dissolved in water then, it does not
give the test for Co3+ ion and NH3.
ii) When complex K4[Fe (CN)6] is dissolved in water then, it does not give a
test for Fe2+, CN- ions because these two ions are present in the coordination
Sphere.
K4[Fe (CN)6] ⇄ 4 K+ + [Fe (CN)6]4-
Complex ion [not ionised]

➢ Distinguish Between Double Salt and Complex Compound: -

Double Salt Complex Compound

i) Individual Components Shows their i) Individual components do not
individual properties. shows their individual properties.
ii) It gives the test of each ion. ii) It does not give the test of each ion
iii) It loses their Identity. in the Coordination Sphere.
iv) They are crystalline in nature. iii) It does not lose their identity.
v) Their crystals have definite iv) They may or may not be e
geometrical shape. crystalline in nature.
1
vi) Ex. Karnalite, Potash alum v) Their shape depends upon
hybridisation of metal ion.
vi) Ex: - [Co(NH3)6]3+, K4[Fe (CN)6]

➢ Terms used in coordination compounds: -

1) Central Metal Ion or Central Metal Atom: -

In the complex, the metal atom or ion attached to ligands through
coordinate bonds in the coordination sphere is called central metal ion /
atom.
E.g.: - [Ni (NH3)6]2+, [Fe (CN)6]3-, [Co(NH3)5C1]2+
In this complex ion, Ni2+, Fe3+, Co3+ are central metal ions.

2) Ligands: -
The species (atoms / ions / molecules) which donate pair of electrons and
forms coordinate bond are called as ligands.
Ligand may be positive, negative or neutral molecules.
a) Positive Ligands: - They have positive charge.
E.g., No+ → Nitrosonium ion
NH₂- NH3+ (N2H5+) → Hydrazinium ion
No₂+ → Nitronium ion.
b) Negative Ligands: -
They have negative charge.
E.g., Cl-, NO2- , CN-, etc.

c) Neutral ligands: -
They have no charge.
E.g., H2O, NH3, R-OH, R-NH2, NH2-OH, NH2-CH2-CH2-NH2

➢ Classification of Ligands: -
a) Positive Ligands: -

Ligand Charge Name of ligand in Complex

NO+ +1 Nitrosonium
NO2+ +1 Nitronium
NH2-NH3+ +1 Hydrazinium

2
b) Neutral Ligands: -

Ligand Charge Name of ligand in Complex

H2O 0 Aquo/ Aqua
NH3 0 Ammine
CO 0 Carbonyl
NO 0 Nitrosyl
C5H5N 0 Pyridine
CH3-NH2 0 Methyl amine
PH3 0 Phosphine
NH2-C-NH2 0 Urea
NH2-CH2-CH2-NH2 0 Ethylenediamine (en)
Ph3P 0 Triphenyl Phosphine
H- -1 Hydrido
O2- -2 Oxo
O22- -2 Peroxo
OH- -1 Hydroxo
F- -1 Fluoro [Flurido]
Cl- -1 Chloro [Chlorido]
Br- -1 Bromo [Bromido]
I- -1 Iodo [Iodido]
CH3COO- -1 Acetato
CN- -1 Cyno
NC- -1 Isocyno
S2- -2 Sulphido
SO32- -2 Sulphito
SO42- -2 Sulphato
NH2- -1 Amido
NH2- -2 Imido
NO3- -1 Nitrato
NO2- -1 Nitro [Nitrito-N]
ONO- -1 Nitrito [Nitrito-O]
N3- -3 Nitrido
N3- -1 Azido
SCN- -1 Thiocynato
NCS -1 Isothiocynato
: NH2-CH2-COO- -1 Glycinato (gly)
S2O32- -2 Thiosulphato
C2O42- -2 Oxalato
CO32- -2 Carbonato
CH3-C=N-O: -1 Dimethylglyoximato

c) Ambident Ligands: -
The ligands that can binds through more than one atom are called as
ambident ligand.
E.g., i) NO2-

3
 M←NO2 M←ONO
Nitrito-N Nitrito-O
-
ii) CN
M←CN M←NC
cyno Isocyno

iii) SCN-
M←SCN M←NCS
Thiocynato Isothiocynato

d) Coordination Number: -
The total number of coordinate bonds attached to central metal ion in the
complex is called as coordination number.
i) [Pt C16]2-
In this, 6 C1- unidentate ligands, attached to Pt therefore C.N. of Pt4+ is
six.
ii) [Fe(C2O4)3]3-
In this, three bidentate ligands (C2O4)2- are attached to Fe therefore C.N.
of Fe3+ is six.
iii) [Fe (EDTA)]2-
In this one hexadentate ligand is attached to Fe2+ therefore C.N. of Fe2+ is
six.

e) Coordination Sphere: -
The space or region where ligands donate electron pair to the central
metal ion and forms coordinate bond in a definite geometrical pattern is
called as coordination Sphere.
It is denoted by '[ ]'.

f) Counter Ion: -
Counter ion may be +ve or -ve.
The +ve counter ion is always kept at LHS of complex ion.
The negative counter ion is always kept at RHS of complex ion.
i) K4 [Fe (CN)6]
The counter ion is K+ and complex ion is [Fe (CN)6]4-.
ii) [Co (NH3)6] Cl3
The counter ion is Cl- and complex ion is [Co (NH3)6]3+.

4
➢ Oxidation states: -

i) K4[Fe (CN)6] ii) [Ni (CO)4]

X+ (-16) = -4 X+(04) =0
X-6 = -4 X+0 = 0
X=2 X =0
Calculate oxidation state of the following (HW)
iii) [Ni (CO)4]
iv) [Cu (CN)4]3-
v) [Co (NH3)3 (NO2)3]
vi) [Co (NH3)6] Cl3
vii) K3 [Fe (CN)5 NO]
viii) [Fe (EDTA)]-
ix) [Cr (en)3]2+
x) [Ni (H2O)2 (en)2]2+
xi) K₂ [AgI4]
xii) [Ag (OH)2]-

➢ Nomenclature of Coordination Compounds (Rules): -

• positive ion is named first followed by negative ion.

E.g.,
i) [Co (NH3)5 C1] Cl2
In this complex, complex ion is +ve ion, it should be named first then -ve
Chloride ion.
ii) K4 [Fe (CN)6]
In this complex, potassium ion is +ve ion is named first then the complex ion
[Fe (CN)6]4-

• Name of Ligands:
The ligands are named in alphabetical order (according to name of ligands
not the prefix).
E.g., [(Pt, Br, Cl, (NO2), (NH3)], in this complex the ligands are named in the
order of Amminebromochloronitrito-N.

5
 • The negative ligands will be end with -O or -ido. The +ve ligands will be end
with 'ium', neutral group have no special ending.
• The number of ligands in the complex is denoted by prefixes di, tri, tetra to
show the number of ligands. But suppose if the name of ligands itself contain
di, tri, tetra...., etc then in such cases following prefixes is used and such
ligands are kept in bracket to avoid confusion.

2 Di Bis
3 Tri Tris
4 Tetra Tetrakis
5 Penta Pentakis
6 Hexa Hexakis

i) [Pt Cl2 (en2)] (NO2)

In this Complex name of ligands is Dichlorobis(ethylenediamine).

ii) [Ni Cl2 (PPh3)2]

In this Complex name of ligands is Dichlorobis(triphenylphosphine).

• Name of metal ion: -

The name of metal ion depends upon the charge on complex ion.
a) If the complex ion carries positive charge or neutral then, metal is named
is normal way.
E.g., i) Co in complex cation is called as cobalt.
ii) Pt in complex cation is called as platinum.
b) If the complex ion carries -ve charge then, the name of metal ends with
suffix -ate.
E.g., i) Co in complex anion is called as cobaltate.
ii) Pt in Complex anion is called as platinate.
c) But for some metals, the Lattin names are used in the complex anion.

Iron [Fe] = Ferrate Silver [Ag] = Argentate

Gold [Au] = Aurate Lead [Pb] = Plumbate

Tin [Sn] = Stannate Copper [Cu] = cuprate

6
• The oxidation state of central metal atom is shown by Roman numbers in the
bracket after the name of metals.
• The prefixes Cis and Trans is used to show same side and opposite side of
geometrical location.
E.g., [Pt (NH3)2 Cl2] Cis and Trans diamminedichloroplatinum (II).

• The name of bridge complex is prefixed by µ.

i) [(NH3)5 Cr-OH-Cr (NH3)5] Cl5
Pentaamine chromium-(III)- µ-hydroxypentaamine chromium-(III) chloride

ii) bis(ethylenediamine)cobalt (III)- µ-imido-µ-hydroxo bis-

(ethylenediamine)cobalt(III) ion

iii) tetraaminecobalt (III)- µ-amido-µ-nitrito-N-tetraamminecobalt (III) nitrate

7
 i) K4 [Fe (CN)6]
K44+ | [Fe (CN)6]4-
No. of ligand → 6 → Hexa
Name of ligand → CN- → Cyno
Complete name of ligand → Hexacyno
Name of metal ion → Ferrate
O.S. of metal ion → x + (-1  6) = -4
x – 6 = -4
x = +2
Complete name of complex → Potassiumhexacynoferrate (II)

➢ Rules for writing the formula of coordination compounds: -

i) The Central atom or ion is placed First.

ii) The ligands are placed in alphabetical order.
iii) The Coordination complex is enclosed in square brackets [ ].
iv) No Space is kept between representation of ionic species within the
formulae.
v) The Charge is indicated outside the square bracket with my number before
sign. E.g., [ Co (NH3)6]3+
vi) The charge of cation is balanced by charge on anion.
E.g., i) Tetraamine aquo Chlorocobalt (III) chloride.
[Co (NH3)4 H2O C1] Cl₂

➢ Sidgwick Electronic Theory: -

This theory is used for the formation of coordination compounds and gave the
concept of EAN. According to this theory, Ligands donate electron pair(s) to
the central metal ion and forms a coordinate bond.

➢ Effective Atomic Number (EAN): -

The total number of electrons associated with central metal ion and electrons
donated by ligands is called as effective atomic number. It is calculated by,
EAN = (Z-n) + (2  C.N.)
Where, Z = Atomic number of metals
n = Oxidation state (no. of electron lost by metal)
C.N. = Coordination number

E.g., [Fe (CN)6]4-

At. No. of Fe (Z) = 26
O.S. of Fe (n) = +2
CN- is unidentate ligand therefore C.N. = 6
8
 ⸫ EAN = (Z-n) + (2 C.N.)
= (26 – 2) + (2  6)
= 24 + 12
= 36
EAN of Fe in [Fe (CN)6]4- is 36.

➢ Effective Atomic Number Rule or EAN Rule: -

The total number of electrons associated with central metal ion and electrons
donated by ligands is equal to the atomic number of nearest zero group
element is called as EAN rule.

Metal Atomic Complex / O.S. C.N. EAN = (Z-n) + (2 

Atom No. Complex ion C.N.)
Fe 26 [Fe (CN)6]4- +2 6 (26-2) + 12 = 36 (Kr)
Co 27 [Co (NO2)6]3+ +3 6 (27-3) + 12 = 36 (Kr)
Cu 29 [Cu (H2O)4]+ +1 4 (29-1) + 8 = 36 (Kr)
Pd 46 [Pd (Cl)6]2- +4 6 (46-4) + 12 = 54 (Xe)
Pt 78 [Pt (NH3)6]4+ +4 6 (78-4) + 12 = 86 (Rn)
Fe 26 [Fe (CN)6]3- +3 6 (26-3) +12 = 35
Cu 29 [Cu (NH3)4]2+ +2 4 (29-2) + 8 = 35
Ni 28 [Ni (NH3)4]2+ +2 6 (28-2) + 12 = 38
Pt 78 [Pt (NH3)4]2+ +2 4 (78-2) + 8 = 84
Ni 28 [Ni (CO)4] 0 4 28 + 8 = 36
Zn 30 [Zn (NH3)4]2+ +2 4 (30-2) + 8 = 36
Co 27 [Co (NH3)6]3+ +3 6 (27-3) + 12 = 36

➢ Drawbacks of Sidgwick’s Theory: -

i) This theory does not explain the stability of complexes which does not
obey EAN rule.
ii) This theory does not explain the directional nature of coordinate bond.

9
➢ Werner’s Theory of Coordination: -

This theory is used to explain the nature of bonding in Complex Compounds.

According to this theory,
i) Each metal ion has two types of valancies:
a) Primary valency b) secondary valency
ii) Primary valency represent oxidation state of metal ion and it is ionisable
and it is denoted by dotted line.......
iii) Secondary valency represents coordination number of metal ion. It is non
ionisable and it is denoted by solid line
iv) Metal ion satisfy both the valancies.
v) Secondary valency of metal ion is fixed. It is directional in nature,
therefore, it represents geometry of complex.
To distinguish two types of valancies, Werner introduced square bracket ‘[ ]’
The species present in square bracket are non-ionisable while outside the
square bracket are ionisable.

1. CoCl3.6NH3: -
This complex contains six NH3 groups which satisfy six secondary valancies
and these Cl- ions which satisfy primary valancies. Therefore, complex may
be formulated as [Co (NH3)6] Cl3.

2. CoCl3.5NH3: -
This Complex contain 5 NH3 groups which satisfy five Secondary valancies.
But secondary valency of cobalt is six. Therefore, one of the secondary
valency is satisfied by one Cl- ion.
The primary Valency of cobalt is three, which satisfy three Cl - ions. This
shows that one of the Cl- ion satisfy both primary and secondary valancies.
Therefore, this complex may be formulated as [Co (NH3)5Cl] Cl2.

10
3. CoCl3.4NH3: -
This Complex Contain four NH3 group which satisfy four Secondary
Valancies. But secondary valency of cobalt is six. Therefore, two secondary
valancies are satisfied by two Cl- ions. The primary valency is three which is
satisfied by three C1 ions. This shows that two Cl- ions satisfy both primary
and secondary valancies. Therefore, the complex may be formulated as;
[Co (NH3)4 C12] Cl.

4. CoCl3.3NH3: -
This complex contains three NH3 groups which satisfy three secondary
valancies. But secondary valency of cobalt is six. Therefore, three secondary
valancies are satisfied by three Cl- ions. The primary valency is three which
is satisfied by three Cl- ions. This shows that three Cl- ions satisfy both
primary and secondary valancies. Therefore, the complex may be
formulated as [Co (NH3)3 C13].

➢ Experimental Verification of Werner's Theory: -

11
 According to Werner’s theory, primary valency is ionisable while secondary
valency is non-ionisable. This can be verified experimentally by two
methods:
i) Precipitation method
ii) Conductivity method

• Precipitation Method: -

a) For [Co (NH3)6] Cl3: -

When excess of AgNO3 reacts with [Co (NH3)6] Cl3 gives precipitation of
three molecules of AgCl, which corresponds to three Cl- ions in ionisation
sphere.

[Co (NH3)6] Cl3 + AgNO3 → [Co (NH3)6]3+ + 3AgCl ↓

excess

When HCl reacts with [Co (NH3)6] C13, no reaction takes place. This
indicate that NH3 molecules are not removed by HCl. All NH3 molecules are
present in coordination sphere and satisfy secondary valency.

b) For [Co (NH3)5 C1] Cl2: -

When excess of AgNO3 reacts with [Co (NH3)5Cl] gives precipitation of two
molecules of AgCl which corresponds to two Cl- ions in ionisation sphere.

[Co (NH3)5Cl] Cl2 + AgNO3 → [Co (NH3)5Cl]2+ + 2AgCl ↓

excess

when HCl reacts with [Co (NH3)5Cl] Cl2, no reaction takes place.

c) For [Co (NH3)4Cl2] Cl: -

[Co (NH3)4Cl2] Cl + AgNO3 → [Co (NH3)4Cl2] + + AgCl ↓
excess

d) For [Co (NH3)3 Cl3]: -

[Co (NH3)3 Cl3] + AgNO3 → No Reaction
excess

➢ Conductivity Method: -

The conductivity of solution depends upon number of ions.

The number of ions and molar conductivity is

12
 Complex Complex Ions No. of Molar
Ions Conductivity
[Co (NH3)6] Cl3 [Co (NH3)6]3+ , 3Cl- 4 390 Mho-1Mol-1
[Co (NH3)5 Cl] Cl2 [Co (NH3)5 Cl]2+ , 2Cl- 3 260 Mho-1Mol-1
[Co (NH3)4 Cl2] Cl [Co (NH3)4 Cl2] +, Cl- 2 102 Mho-1Mol-1
[Co (NH3)3 Cl3] [Co (NH3)3 Cl3] 0 0

➢ Valence Bond Theory [VBT] of Transition Metal Complexes: -

This theory was developed by Pauling in 1931.

• Postulates / Assumptions / salient features of VBT: -
i) The metal atom or ion present in the complex provide definite number of
vacant orbitals like s, p, d for the formation of coordinate bonds with ligands.
ii) The number of vacant orbitals provided by central metal ion is equal to
coordination number.
iii) These vacant orbitals undergo hybridisation and forms same number of
hybrid orbitals.
iv) Each ligand donates pair of electrons to the vacant orbitals.
v) The vacant orbitals of metal ion overlap with filled orbitals of ligands and
forms coordinate bond between metal and ligand.
vi) The geometry of metal ion depends upon hybridisation of metal orbitals.

Types of Hybridisations Shape of Complex

sp Linear
sp2 Trigonal Planer
sp3 Tetrahedral
dsp2 Square Planer
sp3d Trigonal Bipyramidal
dsp3 Square Pyramidal / TBP
sp3d2 Octahedral
d2sp3 Octahedral
sp3d3 Pentagonal Bipyramidal

vii) larger is the overlapping stronger is the bond.

viii) If inner d-orbitals [(n-1) d] are used for hybridisation then, complex is
called as inner orbital complex.
ix) If outer d-orbitals [nd] are used for hybridisation then complex is called
as outer orbital complex.
13
 x) The non-bonding electrons are arranged according to Hund's rule.
xi) But in presence of Strong ligands like CO, CN, NO₂, en, NH3, the
electrons can be pair up against Hund's Rule.
xii) The order of strength of ligands is according to spectrochemical Series.
CO > CN- > NO₂- > en > NH3 > Pyridine > EDTA4- > NCS- > H2O > C₂O42- >
OH- > F- > NO3- > Cl- > SCN- > I-.
xiii) If central metal ion of complex contain unpaired electrons shows
paramagnetic property while paired electrons shows diamagnetic property.

• Magnetic Properties of Complexes: -

The complex which contains unpaired electrons is called paramagnetic
complex or substance or high spin complex or outer orbital complex.
While the complex which contain paired electrons (↑↓) are Called as
diamagnetic complex / compound or low spin complex or inner orbital
complex.
The magnetic properties of complexes are calculated by using magnetic
moment (µ) by formula;
µ = √ n (n+2) = B.M.
where, µ = magnetic moment
n = No. of unpaired electrons
B.M. = Bohr Magneton (unit of magnetic moment)
This formula is also called as ‘spin only formula’.

No. of Unpaired Electrons Magnetic Moment (BM)

1 1.73
2 2.83
3 3.87
4 4.90
5 5.92

➢ Geometry of Coordination Compounds: -

• Complexes with d1d2d3 configuration: -

When central atom contains 1,2, or 3 electrons and occupy first three d-
orbitals and remaining two orbitals remain vacant. The two vacant 3d-
orbitals hybridised with one (4S) and three (4P) orbitals gives d2sp³ hybrid
orbitals and forms octahedral complex.

Formation of [Cr (NH3)6]3+ ion

14
 Atomic No. of Cr = 24
Oxidation State of Cr is +3.
Electronic configuration of Cr3+ is 3d3.

3d 4s 4p
↑ ↑ ↑

These six vacant orbitals undergo d2sp3 hybridisation.

3d
↑ ↑ ↑
d2sp3 hybrid orbitals

In the formation of [Cr (NH3)6]

[Cr (NH3)6]3+ ↑ ↑ ↑      
d2sp3 hybridisation
The complex is formed by d²sp3 hybridisation with octahedral geometry. It
contains three unpaired electrons therefore it is paramagnetic and high Spin
complex.
• Complexes with d4, d5, d6 configuration: -

The electronic configuration in ground state is: -

3d4 ↑ ↑ ↑ ↑ One Orbital Vacant

3d5 ↑ ↑ ↑ ↑ ↑ No Vacant Orbital

3d6 ↑↓ ↑ ↑ ↑ ↑ No Vacant Orbital

They can form two types of complexes;

i) Inner orbital complexes involving d2sp3 hybridisation.
ii) Outer orbital complexes involving sp3d2 hybridisation.

i) Inner orbital complexes involving d2sp3 hybridisation.

15
This type of complexes is formed with strong field ligands which pair up
electrons and makes two d-orbitals vacant for d2sp3 hybridisation.
Formation of [Mn (CN)6]3- ion (d4-system)
Atomic number of Mn = 25
Oxidation State of Mn = +3
Electronic Configuration of Mn3+ = 3d44s04p0
3d 4s 4p
Ground State → ↑ ↑ ↑ ↑
As CN- ion is strong ligand it pairs up 3d electrons. Therefore, electronic
configuration in excited state is;
3d 4s 4p
↑↓ ↑ ↑

These six vacant orbitals undergo d2sp3 hybridisation.

In the formation of [Mn (CN)6]3-

↑↓ ↑ ↑      

The complex is formed by d2sp3 hybridisation with octahedral geometry. It

contains two unpaired electrons therefore it is paramagnetic and high spin
complex.

Formation of [Fe (CN)6]3- ion (d5-system)

Atomic number of Fe = 26
Oxidation State of Fe = +3
Electronic Configuration of Fe3+ = 3d54s04p0

3d 4s 4p
↑ ↑ ↑ ↑ ↑

As CN- ion is strong ligand so it pairs up 3d electrons. Therefore, electronic

configuration in excited state is;
3d 4s 4p
↑↓ ↑ ↑

These six vacant orbitals undergo d2sp3 hybridisation.

3d
↑↓ ↑ ↑
16
In the formation of [Fe (CN)6]3-

↑↓ ↑ ↑      

The complex is formed by d2sp3 hybridisation with octahedral geometry. It

contains one unpaired electron therefore it is paramagnetic and high spin
complex.

ii) Outer orbital complexes involving sp3d2 hybridisation.

It involves one 4s, three 4p and two 4d orbitals. This type of complexes is
formed with weak field ligands.
Formation of [Cr (H2O)6]2+ ion (d4-system)

Atomic number of Cr = 24
Oxidation State of Cr = +2
Electronic Configuration of Cr3+ = 3d4
3d 4s 4p 4d
↑ ↑ ↑ ↑

As H2O is weak ligand so it does not pair up 3d electrons. Therefore, ligands

use outer six orbitals and undergoes sp3d2 hybridisation.
3d 4s 4p 4d
↑ ↑ ↑ ↑
sp3d2 hybrid orbitals
In the formation of [Cr (H2O)6]2+ is;

3d
↑ ↑ ↑ ↑      

The complex is formed by sp3d2 hybridisation with octahedral geometry. It

contains four unpaired electrons therefore it is paramagnetic and high spin
complex.
H.W.
1) Formation of [FeF6]3-
2) Formation of [Co (H2O)6]2+
3) Formation of [Ni (NH3)6]2+

17
iii) Tetrahedral Complexes with sp3 Hybridisation: -

Formation of [Mn (Br)4]2- ion

Atomic number of Mn = 25
Oxidation State of Mn = +2
Electronic Configuration of Mn2+ = 3d5
3d 4s 4p
↑ ↑ ↑ ↑ ↑
In the formation of [Mn (Br)4]2-
3d 4s 4p
↑ ↑ ↑ ↑ ↑    
The complex is formed by sp3 hybridisation with Tetrahedral geometry. It
contains five unpaired electrons therefore it is paramagnetic and high spin
complex.

iv) Square Planar Complexes with dsp2 hybridisation: -

This type of complexes involves one d-orbital, one s-orbital and two p-orbitals.

Formation of [Ni (CN)4]2-

Atomic number of Ni = 28
Oxidation State of Ni = +2
Electronic Configuration of Ni2+ = 3d8
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑
As CN- ion is strong ligand so it pairs up d-electrons. Therefore, electronic
configuration pf Ni2+ in excited state is;
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑↓
These four vacant orbitals undergo dsp2 hybridisation.

↑↓ ↑↓ ↑↓ ↑↓
dsp2 hybridisation

In the formation of [Ni (CN)4]2-

↑↓ ↑↓ ↑↓ ↑↓    

18
The complex is formed by dsp2 hybridisation with Square Planar geometry. It
contains no unpaired electrons therefore it is diamagnetic and low spin complex.

ii) Formation of [Cu (NH3)4]2+ Complex: -

Atomic number of Cu = 29
Oxidation State of Cu = +2
Electronic Configuration of Cu2+ = 3d9
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑↓ ↑
Now one electron from 3d orbital is promoted to 4p orbital and undergoes dsp2
hybridisation.
In the formation of [Cu (NH3)4]2+

↑↓ ↑↓ ↑↓ ↑↓     ↑
dsp2 hybridisation

The complex is formed by dsp2 hybridisation with Square Planar geometry. It

contains one unpaired electron therefore it is paramagnetic and high spin
complex.

➢ Isomerism in Coordination Compounds: -

The compound having Same molecular formula but different structural

formula is called as isomer and this phenomenon is called as isomerism.
There are two main types of isomerism in coordination compounds;
i) Structural Isomerism
ii) Stereo Isomerism → a) Geometrical Isomerism
b) Optical Isomerism

• Structural Isomerism: -
The Compound having some molecular formula but different structural
formula (different arrangement of ligands) is called as structural isomerism.
It is divided into four types:
a) Linkage isomerism
b) Ionisation isomerism
c) Coordination isomerism
d) Solvated or Hydrated isomerism

i) Linkage Isomerism: -
In this type of isomerism, same ligand is bonded to central metal atom through
different atoms.
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The ligand that can bind / link through more than one atom is called as
ambident ligand.
E.g., CO, CN-, SCN-, NO2-
a. NO2- is bonded through N-atom or O-atom
M ← NO2- M ← O-NO-
(Nitrito-N) (Nitrito-O)

b. CN- is bonded through C-atom or N-atom

M ← CN- M ← NC-
(cyno) (Isocyno)

ii) Ionisation Isomerism: -

In this type of isomerism there is an exchange of ions inside and outside of the
coordination sphere.
E.g., a) [Co (NH3)5 Br]SO4 and [Co (NH3)5 SO4] Br
Red violet Red
E.g., b) [Pt (NH3)4 Cl2] Br2 and [Pt (NH3)4 Br2] SO4

c) [Co (en)2 NO2 Cl] SCN

[Co (en)2 NO2 SCN] Cl
[Co (en)2 SCN Cl] NO2

iii) Coordination Isomerism: -

In this type of isomerism there is interchange of ligands between positive and
negative ions.
E.g., a) [Co (NH3)6]3+ [Cr (CN)6]3- and [Cr (NH3)6]3+ [Co (CN)6]3-
b) [Cu (NH3)4] [Pt Cl4] and [Pt (NH3)4] [Cu Cl4]

iv) Solvated or Hydrated Isomers: -

In this type of isomerism there is an exchange of water molecule inside and
outside of the coordination sphere.
E.g., [Cr (H2O)6] Cl3
[Cr (H2O)5 Cl] Cl2.H2O
[Cr (H2O)4 Cl2] Cl.2H2O
[Cr (H2O)3 Cl3] .3H2O

• Stereo Isomerism: -
The compound having same molecular formula but different arrangement
around central metal atom / ion is called as stereo isomerism.
There are two types of stereo isomerism: -
i) Geometrical Isomerism
ii) Optical Isomerism
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❖ Geometrical Isomerism: -
The isomerism having same molecular formula but different arrangement of
ligands around the central metal atom / ion is called as geometrical
isomerism.
When same ligands are at same position then it is called as cis-isomer.
When same ligands are at opposite position then it is called as trans-isomer.
The geometrical isomerism is possible only in the complexes with
coordination number 4 or greater than 4.

1) Geometrical Isomerism in Octahedral Complexes: -

Coordination Number = 6
Cis position = 1-2, 1-3, 2-3, 3-6, 6-4, 3-4, 4-5, 5-2, 1-4 and 5-1
Trans position = 1-6, 2-4, and 3-5

The octahedral complexes of the type Ma4b2, Ma4bc, Ma3b3, M(AA)2b2 shows
cis and trans isomers.
a) Ma4b2, [Co (NH3)4Cl2] + and Ma4bc, [Co (NH3)4Cl NO2] + type complex: -
This type of complexes exists in cis and trans isomerism.

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b) Ma3b3, [Co (NH3)3 Cl3] type complex: -
In this type of complex, when three same ligands are at same position of
octahedron then it is called as facial or fac isomer.
When three same ligands are at three corners of square planar then it is called as
meridional or Mer isomers.
Fac isomer = same ligands at 1, 2, 3 position and another three same ligands at
4, 5, 6 position.
Mer isomer = same ligands at 1, 2, 4 position and another three same ligands at
3, 5, 6 position.
Other examples, [Co (NO2)3 (NH3)3], [Rh-Cl3 (Py)3], [Cr (NH3)3 Cl3]

c) Ma2b2c2, [Pt (NH3)2(Py)2Cl2] Type : -

This type of complexes exists in five geometrical isomerism’s out of which
only three can be isolated.

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d) [M(AA)2b2], [Co (en)2Cl2] + Type: -

It shows two types of isomerism i.e., cis and trans.

2) Geometrical Isomerism in Square Planar Complexes: -

Cis position = 1-2, 2-3, 3-4, 4-1
Trans position = 1-3, 2-4

a) Ma2b2, [Pt (NH3)2Cl2] type complex: -

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 b) Ma2bc, [Pt (NH3)2Cl Br] type complex: -

❖ Optical Isomerism: -
✓ The substance which rotates plane polarised light is called optically active
compound.
✓ The compound having same molecular and structural formula but non-super-
imposable mirror image of each other is called as optical isomer, and this
phenomenon is called as optical isomerism.
✓ This type of isomerism is shown by those complexes which do not have any
element of symmetry (i.e., plane of symmetry, line of symmetry and point of
symmetry).
✓ The optical isomers are d, l, and dl type.
✓ The substance which rotates plane polarised light in clockwise direction
(right side) is called as dextro-rotatory or d-isomer.
✓ The substance which rotates plane polarised light in anticlockwise direction
(left side) is called as leavo-rotatory or l-isomer.
✓ The d and l isomer are mirror images of each other and non-superimposable
therefore they are called as enantiomers.
✓ The d and l isomers are optically active.
✓ The equimolar mixture of d-isomer and l-isomer is called as racemic mixture
or dl-isomers, which is optically inactive due to external compensation.
✓ Optical activity is mostly observed in complex compound having
coordination number 4 and 6.

1) Optical Isomerism in Complexes with C.N. = 6

a) Ma2b2c2, [Pt (NH3)2(Py)2Cl2]2+ type complex :-

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 b) Mabcdef, [Pt (Py)(NH3)(NO2)Cl.Br. I]o type complex: -
This type of complex exists in 15 geometrical isomeric forms. Each of
these 15 geometrical isomers exist in d and l isomers and gives total 30
optically active isomers. One of the 15 geometrical isomers is given in
figure,

c) [M(AA)3], [Co(en)3]3+ type complex: -

Where AA is bidentate ligand.

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d) [M(AA)2b2], [Co(en)2Cl2] + type complex: -

2) Optical Isomerism in Complexes with C.N. = 4 (Tetrahedral Complexes)

a) [Mabcd], [As (CH3) (C2H5) (S)(C6H5COO)]2+ type complex: -

b) M(AA)2, [B(C6H4OCHO)2] + type complex: -

3) Optical Isomerism in Complexes with C.N.=4 (Square planar complexes)

E.g., [Pt (NH2-CH(C6H5)-CH(C6H5)-NH2) (NH2-CH2-C(CH3)2-NH2)]2+ ion

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