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Chapter-6
Co-ordination Compounds

This chapter deals with the study of preparation, structure and properties of
coordination compounds. Coordination compounds are the compounds.
containing co-ordinate bond. Coordinate bond is formed by the sharing and
transference of lone pair of electrons between two atoms. The atom which donate
the lone pair of electrons is known as donor and the atom which accept the lone
pair of electron is known as acceptor. Coordinate bond is represented by→
pointing from donor to acceptor.
Eg. Consider the reaction of 𝐶𝑢𝑆𝑂4 and 𝑁𝐻3
𝐶𝑢𝑆𝑂4 + 4 𝑁𝐻3 → [𝐶𝑢(𝑁𝐻3 )4 ] 𝑆𝑂4
The deep blue colour of the complex is due to the formation of above complex.
The structure of the complex is as shown below.

Ligands- Ligands are an atom or group of atoms which are coordinated to the
metal ion of a coordination complex. Eg: 𝑁𝐻3
Classification of ligands: Ligands are classified into three types
1. Monodentate Ligand- This type of ligand can form only one coordinate bond
with the central metal ion of the complex. Eg: 𝑁𝐻3
2. Bidentate Ligand. This type of ligand can form two coordinate bond with the
metal ion of the complex. Eg: Ethylene Dimine 𝐻2 𝑁- 𝐶𝐻2 - 𝐶𝐻2 - 𝑁𝐻2
3. Polydentate Ligand. This type of ligand can form more than two coordinate
bond with the metal ion of the complex. Eg: Ethylene diamine tetra acetic acid
(EDTA)
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It can form six coordinate bonds with the metal ion. Hence it is a hence dentate
ligand Coordination Number: The number of coordinate bond around the metal
ion of a coordination complex is known as coordination number.
Eg: Consider the complex[𝐶𝑢(𝑁𝐻3 )4 ] 𝑆𝑂4
Here coordination number is four
Naming of Coordination Complex (IUPAC System)
The important postulates are following:
1. Positive part of the complex named first followed by ve part or co-ordination
sphere.
2. For the naming of coordination sphere Ligands are named first and then the
metal ion followed by oxidation number of the metal.
3. Oxidation number of the metal ion is indicated by roman numbers like 1. II. III
ete in parenthesis.
4. Ligands are named in the alphabetical orders.
5. The number of monodentate ligands are prefixed by di, tri ete for its numbers
2.3.4, etc.
6. The number of bidentate ligands or poly dentate ligands are prefixed by bis or
tris for its numbers 2.3.4.
7. For a neutral complex sum of all the charges of the metal and ligand will be 0.
8. The name of the ve ligands and in "0".
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9. Following are the name of the neutral ligand

𝐻2 𝑂 − 𝐴𝑞𝑢𝑎 𝑁𝐻3 − 𝐴𝑚𝑚𝑜𝑛𝑖𝑎
𝐶𝑂 − 𝐶𝑎𝑟𝑏𝑜𝑛𝑦𝑙 𝐻2 𝑁 − 𝐶𝐻2 − 𝐶𝐻2 − 𝑁𝐻2 𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑑𝑖𝑎𝑚𝑖𝑛𝑒 [𝑒𝑛]

10. If the complex region (coordination sphere) has a -ve charge. The name of the
metal ends in “atc"
Give the IUPAC name of the following complex

1. [𝑁𝑖(𝐶𝑂)4 ] Tetra carbonyl Nickel (0) /

2. [𝐶𝑢(𝑁𝐻3 )4 ] 𝑆𝑂4 − Tetraamine Copper (11) Sulphate
3. [𝐶𝑜(𝑁𝐻3 )6 ] 𝐶𝑙3 − Hexamine Cobalt (III) Chloride

4. [𝐶𝑜(𝑁𝐻3 )5 𝐶𝑙] 𝐶𝑙2 Pentaamine Chlorido Cobalt (III) Chloride

5. [𝑃𝑡(𝑁𝐻3 )2 𝐶𝑙2 ] Diamine dichlorido Platinum (11)
6. 𝑁𝑎3 [𝐹𝑒(𝐶𝑁)6 ] Sodium Hexa Cyno Ferrate (III)
7. 𝑁𝑎3 [𝐹𝑒(𝐶𝑙)6 ] Sodium hexa chlorido ferrate (III)
8. 𝑁𝑎4 [𝐹𝑒(𝐶𝑁)6 ] Sodium Hexa Cyno Ferrate (III)
−
9. 𝐾3 [𝐴𝑙(𝐶2 𝑂4 )3 ] Pottasium Tris oxalato aluminate (III)
10. K[B𝐹4 − ] Pottasium tetra flurido borate (III)
11. [𝑃𝑡(𝑁𝐻3 )2 𝐶𝑙2 ] 𝑃𝑡𝐶𝑙4 − Diammine dichlorido Platinum (IV) Tetra chlorido
Platinate (11)
(inter changing the oxidation number. First part is the ve and 2 is-ve part)
12. [𝐶𝑟(𝑁𝐻3 )6 𝐶𝑜(𝐶𝑁)6 ] Hexammine chrominum(III) Sodium hexa cyano
cobaltate (II)
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Isomerism in coordination compounds: If two compounds having the same

molecular formula but differ in their properties are called Isomers and that
phenomenon is known as isomerism
Isomerism is then classified into two types
1. Structural isomerism 2. Stereo isomerism
a) lionisation isomerism This type of isomerism is due to difference in the nature
of ions of two complex having same molecular formula
Eg: Consider pentaamine bromide cobalt (III) sulphate and Pentaamine
sulphate cobalt (III) Bromide
[𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟] 𝑆𝑂4 → [𝐶𝑜(𝑁𝐻3 )5 𝐵𝑟]2+ + 𝑆𝑂4 2−
[𝐶𝑜(𝑁𝐻3 )5 𝑆𝑂4 2− ] 𝐵𝑟 → [𝐶𝑜(𝑁𝐻3 )5 𝑆𝑂4 ]+ + Br
The presence of So, ion in the first complex can be identified by adding Bacl
solution and it gives a white precipitate of Ba𝑆𝑂4 but it doesn't give any ppt. by
the addition of Ag𝑁𝑂3 and indicate the absence of bromide ion. But the second
complex gives the pale yellow ppt of AgBr by the addition of Ag𝑁𝑂3 indicate
the presence of Br ion but doesn't gives white ppt by the addition of Bacl indicate
absence of 𝑆𝑂4 2− ion.
b) Hydrate isomerism This type of isomerism is due to difference in the position
of water molecule inside & outside the coordination sphere.
Eg: [𝐶𝑟(𝐻2 𝑂)6 𝐶𝑙3 ] Hex aqua chromium (III) chloride
[𝐶𝑟(𝐻2 𝑂)4 𝐶𝑙2 𝐻2 𝑂 Tetra aqua di chlorido chromium (III) Chloride di hydrate
[𝐶𝑟(𝐻2 𝑂)3 𝐶𝑙3 , 2𝐻2 𝑂 Tetra aqua tri chlorido chromium (III) Tri dihydrate
[𝐶𝑟(𝐻2 𝑂)3 𝐶𝑙3 , 3𝐻2 𝑂 Tri aqua tri chlorido chromium (III) tri hydrate

c) Linkage Isomerism This type of isomerism is due to the difference in the

nature of atom of the ligand which is coordinated to metal ion of a complex.
[𝐶𝑜(𝑁𝐻3 )5 𝑁𝑂2 ] 𝐶𝑙2 Pentaamine N- Nitrito Cobalt (III) Chloride
[𝐶𝑜(𝑁𝐻3 )5 𝑂𝑁𝑂] 𝐶𝑙2 Pentaamine O Nitrito Cobalt (III) Chloride
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In the first complex Nitrogen atom of Nitrito ligand is coordinated to cobalt ion.
But in the second complex oxygen atom of Nitrito ligand is coordinated
to the cobalt ion.
d) Coordmation Isomerism -This type of isomerism is generally found in poly
unclear complexes and obtained by inter changing the ligand with respect to metal
ion.
[𝐶𝑟(𝑁𝐻3 )6 𝐶𝑜(𝐶𝑁)6 ] Hexamine chromium (III) hexa cyano cobaltate (111)
[Co(𝑁𝐻3 )6 ][Cr(𝐶𝑁)6 Hexammine Cobalt (III) hexa cyano chromate (III)

Sterio Isomerism: It is then classified into two types.

a) Geometrical Isomerism Following are the conditions of Geometrical
Isomerism
1. Presence of two different type of ligands
2. Coordination number of the complex is 4 or 6
Eg. [𝑃𝑡(𝑁𝐻3 )2 𝐶𝑙2 ] In the above complex Coordination number is 4. Here if the
two ligands are on the same side of the metal ion isomer is known as cis form and
the same ligand on the opposite side of the metal ion is known as trans form.
Geometrical Isomerism is also called Cis-trans isomerism.

The cis isomer is known as Cis platin and used for the treatment of cancer.
Eg: [𝐶𝑜(𝑁𝐻3 )4 𝐶𝑙2 ] 𝐶𝑙 Here coordination number is 6. The cis and trans
isomer of this complex is shown below.
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b) Optical Isomerism When a plane polarized light is allowed to pass through

certain coordination complexes, the direction of vibration of the particles shift
either towards the right or towards the left. This ability of coordination compound
is known as optical activity and this isomerism is known as optical isomerism. If
the direction of vibration shift towards the right is known as dextro-rotation (d
form) and if the direction of vibration shift towards the left is known as lacvo-
rotation (1 form) The diagrammatic representation of optical isomerism

Following are the condition of Optical isomerism

1. Coordination number of the complex is six
2. Presence of bidentate or poly dentate ligand
3. Presence of non super impossible object and mirror image relationship.
Eg. [𝐶𝑜(𝑒𝑛)3 ]3+ -Tris ethylene diamine cobalt (III) ion. The shape of the complex
is octahedral because it coordination number is 6 (3x2). The non-super impossible
object and mirror image are as shown below.
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Eg: The complex [𝐶𝑜(𝑒𝑛)2 𝐶𝑙2 ]+ It can exist as Cis and trans isomers. The Cis
isomer is optically active because it can form non-super impossible object and
mirror image as shown below.

Trans isomer of the above complex is optically inactive because it can form super
impossible object and mirror image as shown below.

[Pt(en),Cl₂] It can exist the Cis and trans as shown below.

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Here the Cis isomer is optically active because it can form non super impossible
object and mirror image relationship

Valance Bond Theory of Coordination Compound (VB Theory)

Following are the important postulates of VB theory.
1. The central metal atom losses requisite number of electron to become a cation.
2. The central metal ion makes hybrid orbitals which is equal to coordination
number of complex.
3. The metal ligand bond is formed by the overlapping of the hybrid orbitals of
metal ions with orbitals containing lone pair of electron of the ligand
4. If the hybridization of the metal ion is s 𝑃3 the shape is tetrahedral. If it is ds𝑃2
the shape is square plannar and for gamma S𝑃3 𝑑 2 and 𝑑 2 𝑠𝑃3 hybridisation the
shape of the complex is octahedral.
5. If the metal ion contains lone pair of e the complex is para magnetic and the
metal ion countains completely paired electron then the complex is diamagnetic.
S 𝑷𝟑 hybridisation -The process of mixing up of one S orbital and three p orbital
from an outermost shell of an atom to form 4 equivalent orbitals is known as s
𝑃3 hybridisation and the resulting orbitals are called s 𝑃3 hybrid orbitals
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Eg: [Ni (Co) 4 ] Tetra Carbonyl Nickel (0)

Here atomic number of Nickel is 28 –
1𝑆 2 2𝑆 2 2𝑝6 3𝑆 2 3𝑝6 3𝑑8 4𝑆 2 4𝑝6 𝑜𝑟 [𝐴𝑟] 3𝑑 8 4𝑆 2 4𝑝6
The box diagram representation of this complex is as shown below

The above complex is paramagnetic due to the presence of completely 2 unpaired

electron. The shape of the complex is tetra hedral.
𝒅𝟐 S𝒑𝟑 hybridisation – The process of mixing up of two of the inner d orbitals,
one s orbital and three p orbitals from the outermost shell of an atom to form 6
equivalent orbitals is known as 𝒅𝟐 S𝒑𝟑 hybridization
Eg . [𝐶𝑜(𝑁𝐻3 )5 ]3+ hexamine cobalt (III) ion.
Electronic configuration of 𝑪𝒐𝟑+ ion is [Ar]3𝑑 6 4𝑆 0 4𝑝0 4𝑑 0
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The above compound is diamagnetic due to the presence of completely paired

electron. Shape of the complex is octahedral
S𝒑𝟑 𝒅𝟐 hybridisation - The process of mixing of one S orbital, three p orbitals
and two of the outermost d orbitals of an atom to form 6 equivalent orbitals is
known as S𝒑𝟑 𝒅𝟐 hybridisation. Eg: [𝐶𝑜(𝐹)6 ]3− Hexa flurido cobaltate (III)
Here oxidation number of cobalt is +3. The electronic configuration of 𝑪𝒐𝟑+ ion
is [Ar]3𝑑 6 4𝑆 0 4𝑝0 4𝑑 0
Box diagram representation is as follows: