5.

COORDINATION COMPOUNDS
Quick Revision Points
Werner’s theory
In coordination compounds, metals show two types of linkages (valences)-primary and
secondary.
Primary valences Secondary valences
are ionisable and satisfied by negative are non-ionisable and satisfied
ions. by neutral molecules or negative
ions
It is equal to the coordination
number
Difference between a double salt and a complex salt
Double salts Complex salts
Dissociate into simple ions completely Do not dissociate into simple
when dissolved in water. ions in water
e.g. Mohr’s salt, FeSO4.(NH4)2SO4.6H2O e.g. K4[Fe(CN)6].Complex ion
[Fe(CN)6]4- does not dissociate
into Fe2+ and CN− ions.
Important Terms
(a)Coordination entity - A coordination entity constitutes a central metal atom or ion
bonded to a fixed number of ions or molecules.
e.g., [CoCl3(NH3 )3] is a coordination entity.
(b)Central atom/ion - In a coordination entity, the atom/ion to which a fixed number of
ions/groups are bound in a definite geometrical arrangement around it, is called the
central atom or ion.
(c) Ligands -Ions or molecules bound to the central atom/ion in the coordination entity
are called ligands.
Unidentate ligand Is bound to a metal ion through a single
donor atom. e.g.,Cl−,H2O or NH3
Didentate ligand Is bound to a metal ion through two donor
atoms. e.g.,H2NCH2CH2NH2 (ethane-
1,2-diamine) C2O42− (oxalate ion)

Polydentate ligand It is linked to a metal ion through several

donor atoms.
e.g., Ethylenediaminetetraacetate ion
(EDTA ) is a hexadentate ligand.
Chelate ligand When a di or polydentate ligand uses its
two or more donor atoms to bind to a
single metal ion, it is said to be a chelate
ligand.
Ambidentate ligand. Can bind to the central metal atom
through any of the two donor atoms present
in it. e.g., NO2−, SCN−,CN-

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(d) Coordination number – It is the number of ligand donor atoms to which the metal is
directly bonded.
[Ni(NH3)4]2+ - the coordination number of Ni is 4
[Fe(C2O4)3 ]3– - the coordination number of Fe is 6
(e) Homoleptic and heteroleptic complexes
Homoleptic complexes Heteroleptic complexes
Metal is bound to only one kind of Metal is bound to more than one kind
donor groups e.g.,[Co(NH3)6]3+ of donor groups. e.g.,[Co(NH3)4Cl2]+

IUPAC names of some coordination compounds

1 K2[Zn(OH)4] Potassium tetrahydroxozincate(II)
2 K3[Al(C2O4)3] Potassium trioxalatoaluminate(III)
3 [Pt(NH3)BrCl(NO2)]– Amminebromidochloridonitrito-N-platinate(II) ion
4 [CoCl2(en)2]Cl Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride
5 [Ni(CO)4] Tetracarbonylnickel(0)
Isomerism in Coordination Compounds
Stereoisomerism
Stereoisomers have the same chemical formula and chemical bonds but they have
different spatial arrangements.
(i) Geometrical isomerism (ii) Optical isomerism
Geometrical Isomerism -This type of isomerism arises in heteroleptic
complexes due to different possible geometric arrangements of the ligands
COORDINATION [Ma2b2]
NO-4 [Pt(NH3)2Cl2]
(Square planar
complexes)
Tetrahedral complexes do not show geometrical isomerism.
Reason: The relative positions of the unidentate ligands attached to the
central metal atom are the same with respect to each other
COORDINATION [Ma2b4 ]
NO 6 [Co(NH3)4Cl2 ]+
(Octahedral
complexes)

[Ma-a2b2]
[CoCl2(en)2]+

[Ma3b3]
[Co(NH3)3(NO2)3]

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 Optical Isomerism: Optical isomers are mirror images that cannot be
superimposed on one another and are called as enantiomers.
Optical isomers of [Co(en)3] +3

Optical isomers of [CoCl2(en)2] +

Trans isomer of [CoCl2 (en)2] + does not show optical activity as it has a plane of
symmetry.

Structural isomerism
Structural Isomerism: These are isomers which differ in the structural arrangement of
ligands around the central atom.
Ionisation Arises when the counter ion in a complex salt is itself a
Isomerism potential ligand and can displace a ligand
[Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4.
Linkage Seen in a coordination compound containing ambidentate
Isomerism ligand
[Co(NH3)5(NO2)]Cl2 and [Co(NH3)5(ONO)]Cl2
Coordination Arises from the interchange of ligands between cationic
Isomerism and anionic entities
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
Solvate Arises due to the presence of solvent molecules as a ligand
Isomerism or as free solvent molecules in the crystal lattice.
[Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O

Bonding in Coordination Compounds

Valence Bond Theory
According to this theory, the metal atom or ion under the influence of ligands can use its
(n-1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals
of definite geometry.

Complex/ion Configuration Hybridisation Geometry No of Magnetic

of the metal of the metal unpaired behaviour
ion/atom ion/atom electrons
[NiCl4] 2- Ni2+ - 3d84s0 sp3 Tetrahedral 2 Paramagnetic
[Ni(CO)4] Ni -3d84s2 sp3 Tetrahedral 0 Diamagnetic
[Ni(CN)4] 2- Ni2+ - 3d84s0 dsp2 Square 0 Diamagnetic
planar

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 [Co(NH3)6] +3 Co+3 - 3d64s0 d2sp3 Octahedral 0 Diamagnetic
(Inner
orbital
complex -
3d used)
[CoF6 ]3- Co+3 - 3d64s0 sp3d2 Octahedral 4 Paramagnetic
(Outer
orbital
complex -
4d used)
Crystal Field Theory
(a)Crystal field splitting in octahedral coordination entities

The splitting of degenerate levels due to the presence of ligands in a definite geometry is
termed as crystal field splitting
Ligands arranged in a series in the order of increasing field strength is termed as
Spectrochemical series
Weak field ligands Strong field ligands
∆o < P ∆o > P
Form high spin complexes Form low spin complexes
d4 Configuration

t2g3eg1
t2g4eg0
(b) Crystal field splitting in tetrahedral coordination entities

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Colour of coordination compounds
The crystal field theory attributes the colour of the coordination compounds to d-d
transition of the electron.
In the absence of a ligand, crystal field splitting does not occur and hence the substance
is colourless. For example, the removal of water from [Ti(H2O)6 ]Cl3 on heating renders it
colourless.
Bonding in Metal Carbonyls
In metal carbonyls, the M–C σ bond is formed by the donation of lone pair of electrons on
the carbonyl carbon into a vacant orbital of the metal. The M–C π bond is formed by the
donation of a pair of electrons from a filled d orbital of metal into the vacant antibonding
π* orbital of carbon monoxide. The metal to ligand bonding creates a synergic effect which
strengthens the bond between CO and the metal.

Multiple Choice Questions

1 Write the no. of ions produced from the complex K4[Fe(CN)6] in
solution
(A) 2 (B) 5
(C) 4 (D) 1
2 The denticity of EDTA ligand is
4-

(A) 6 (B) 3
(C) 4 (D) 2
3 Of the following complexes, which one will show linkage isomerism?
(A) [Cr(NH3)6][Co(en)3] (B) [Cr(NH3)6]Cl3

(C) [Cr(en)3]Cl3 (D) [Cr(NH3)5NO2]Cl2

4 The crystal field splitting energy for octahedral and tetrahedral

complexes is related as
(A) Δt = 2/9 Δo (B) Δo = 2/9 Δt
(C) Δt = 4/9 Δo (D) Δo = 4/9 Δt
5 The type of isomerism shown by the complex [CoCl2(en)2] is
(A) Geometrical isomerism (B) Ionization isomerism
(C) Coordination isomerism (D) Linkage isomerism
6 The coordination number and oxidation state of Cr in K3[Cr(C2O4)3]
are respectively
(A) 3 and +3 (B) 3 and 0
(C) 6 and +3 (D) 4 and +2
7 The geometry and magnetic behaviour of the complex [Ni(CO)4] are
(A) Square planar and (B) Tetrahedral and diamagnetc
paramagnetic
(C) Square planar and (D) Tetrahedral and
diamagnetic paramagnetic

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