[LECTURE NOTE - CHEMISTRY [SECOND YEAR]

CHAPTER - 09
CO-ORDINATION COMPOUNDS

The transition metals form a large number of complex compounds in which the metal atoms/ions are bound
to a number of anions or neutral molecules. Such compounds are called co-ordination compounds. The
chemistry of co-ordination compounds is an important area of modern inorganic chemistry and provides
insights into the chemical bonding, molecular structure and functioning of vital components of biological
systems. Chlorophyll, haemoglobin and vitamin B12 are co-ordination compounds of magnesium, iron and
cobalt respectively. A variety of metallurgical processes, industrial catalysts and analytical reagents involve
the use of coordination compounds. Co-ordination compounds also find applications in electroplating, textile
dyeing and medicinal chemistry.
Werner’s theory of co-ordination compounds
The first ideas about the structures of co-ordination compounds were formulated by Alfred Werner, a
swiss chemist. He prepared and characterised a large no.of co-ordination compounds and studied their
physical and chemical behaviour. Werner proposed the concept of a primary valence and a secondary
valence for a metal ion. Binary compounds like CrCl3, CoCl2 and PdCl2 have primary valence of 3,2 and 2
respectively. Werner found that in a series of compounds of CoCl3 and NH3, only some of the chloride ions
could be precipitated as AgCl on adding excess of AgNO3 solution, but some others could not be
1 mole CoCl3.6NH3(yellow) gave 3 mol AgCl
1 mole CoCl3.5NH3(purple) gave 2 mol AgCl
1 mol CoCl3.4NH3 (green) gave 1 mol AgCl
1 mol CoCl3.4NH3 (violet) gave 1 mol AgCl
These observations together with the results of conductivity measurements in solution can be explained
if (i)six groups in all, either Cl– ions or NH3 molecules or both, remain bonded to the cobalt ion during the
reaction and (ii) the compounds are formulated as shown below.
Formulation of CoCl3–NH3 complexes
Colour Formula Conductivity in solution correspons to
Yellow [Co(NH3)6]3+3Cl– 1 : 3 electrolyte
Purple [Co(NH3)5Cl]2+2Cl– 1 : 2 electrolyte
Green [Co(NH3)4Cl2]++Cl– 1 : 1 electrolyte
Violet [Co(NH3)4Cl2]+Cl– 1 : 1 electrolyte
Although the last two compounds above have identical empirical formula CoCl3.4NH3, they have different
properties they are therefore isomers.

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These observations led Werner to propound his theory of coordination compounds. The main postulates
are:
1. In coordination compounds, metals show two types of linkages (valences)-primary and secondary.
2. The primary valences are normally ionisable and are satisfied by negative ions.
3. The secondary valences are non ionisable. These are satisfied by neutral molecules or negative ions
or both. The secondary valence of a metal is equal to its co-ordination number and is fixed for a metal.
4. The ions/groups bound by secondary linkages to the metal have characteristic spatial arrangements
corresponding to different coordination numbers.
In the modern theory, such spatial arrangements are called co-ordination polyhedra. The species
within the square bracket are called co-ordination entities and the ions outside the square bracket
are called counter ions.
Werner further postulated that octahedral, tetrahedral and square planar shapes are more common in
coordination compounds of transition metals. Thus [Co(NH3)6]3+, [Co(NH3)5Cl]2+ and [Co(NH3)4Cl2]+
are octahedral entities, [Ni(CO)4] is tetrahedral and [PtCl4]2– is square planar.
Difference between a double salt and a complex
Both double salts as well as complexes are formed by the combination of two or more stable compounds
in stoichiometric ratio. However, they differ in the fact that double salts such as carnallite
KCl.MgCl2.6H2O, Mohr’s salt FeSO4.(NH4)2SO 4.6H2O, potash alum K2SO 4.Al2(SO4)3.24H2O etc
dissociate completely into simple ions when dissolved in water. But complex ions such as [Fe(CN)6]4–
of K4[Fe(CN)6] do not dissociate into Fe2+ and CN– ions.

FeSO 4 .  NH 4  2 SO 4 .6H 2O 

water
 Fe 2 (aq)  2NH 4 (aq)  2SO 42  (aq)  6H2 O
(a double salt)
water
[Fe(CN) 6 ]4   no dissociation
(a complex ion)
Ligands
The ions or molecules bound to the central metal atom/ion in the coordination entity are called ligands.
These may be simple ions like Cl–, small molecules like H2O or NH3, larger molecules like NH2–CH2–
CH2-NH2 or even macromolecules such as proteins. Some coordination compounds may contain
positively charged ligands also. Eg. of cationic ligands are hydrazinium ion NH2– NH 3 , nitrosonium
ion NO+ etc.
When a ligand is bound to a metal atom/ion through a single donor atom as with Cl–, NH3 or H2O, the
ligand is said to be monodentate or unidentate. When a ligand can bind through two donor atoms as
in NH2–CH2–CH2–NH2(ethylene diamine or ethane-1,2-diamine) or C2 O 24  (oxalate), the ligand is said
to be bidentate or didentate and when several donor atoms are present in a single ligand as in edta4–
, the ligand is said to be polydentate (edta4–, for example, is hexadentate)
When a di-or polydentate ligand uses its two or more donor atoms to bind a single metal ion, it is said
to be a chelate ligand. The no.o f ligating groups is called the denticity of the ligand. Such complexes,
called chelate complexes are more stable then similar complexes containing unidentate ligands.
A ligand which can ligate through two different atoms is called ambidentate ligand. Examples of such
ligands are NO 2 and SCN– ions. NO 2 can coordinate either through its N or its O.

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O
M M O N O
N
O
Nitrite-N-complex Nitrito-O-complex

Similarly SCN– ion can coordinate through its S or N atom.

Co-ordination number
The C.No of a metal atom/ion in a complex is the no.of ligand donor atoms to which the metal is
directly bonded. For example in the complex ions[PtCl6]2– and [Ni(NH3)4]2+ the C. No of Pt and Ni are
6 & 4 respectively. In the complex ions [Co(en)3]3+ and [Fe(C2O4)3]3–, the C. No of both Co and Fe is 6
because en and C 2 O24  are bidentate ligands.
Homoleptic and heteroleptic complexes
Complexes in which a metal is bound to only one kind of ligands eg.[Co(NH3)6]3+, [Ni(CO)4] are known
as homoleptic. Complexes in which a metal is bound to more than one kind of ligands eg [Co(NH3)4Cl2]+
are known as heteroleptic.
IUPAC nomenclature of coordination compounds
Isomerism in coordination compounds
Two principal types of isomerism are known among coordination compounds. Each of these can be
further subdivided.
A) Structural isomerism
1. Linkage isomerism : This kind of isomerism arises in a coordination compound containing an
ambidenate ligand. eg. The ligand NO 2 (nitrite ion) can bind itself to the central metal either through
its N(–NO2) (nitrito–N–complex) or its O (–ONO) (nitrito-O-complex) giving rise to two isomers which
are called linkage isomers.
Eg . [Co(NH3)5(NO2]Cl2 and [Co(NH3)5(ONO)]Cl2
(yellow) (red)
2. Ionisation isomerism : This form of isomerism arises when the counter ion in a complex salt is
itself a potential ligand and can displace a ligand which can then become the counter ion.
Eg: [Co(NH3)5Br]SO4 and [Co(NH3)5(SO4)]Br are ionisation isomers.
3. Co-ordination isomerism : Arises when both the cation and the anion of a coordination compound
are complexes and the ligands in them may interchange positions.
Eg : [Cu(NH3 ) 4 ] [PtCl 4 ] and  Pt(NH3 ) 4   CuCl 4 
cation anion cation anion

Another eg. is  Cr  en 3   Co  CN 6  and  Co  en 3   Cr  CN 6 

cation anion cation anion
4. Solvate isomerism : This form of isomerism is known as hydrate isomerism when the solvent
involved is water. Solvate isomers differ by whether or not a solvent molecule is directly bonded to the
metal ion or merely present as free solvent molecules in the crystal lattice.

Eg : Cr  H 2 O   Cl3 and Cr  H2 O 5 Cl  Cl2 .H2 O are hydrate isomers.

(violet)  grey  green 

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B) Stereoisomerism
Stereoisomers have the same chemical formula and chemical bonds but they have different spatial
arrangement.
1. Geometrical isomerism : A few typical examples of coordination entities in which geometric
isomerism is possible are given below.

C.NO Shape Type Example No. of ge ome tric is ome rs

4 Square planar [MA 2B 2] [Pt(NH 3)2Cl2] 2(cis and trans)
4 Square planar [MAB 2C] [P t(NH 3)Cl2(P y)] 2(cis and trans)
4 Square planar [MABCD] [Pt(NH 3)BrCl(Py)] 3 (2 cis and 1 trans)
4 Square planar [M(A-B) 2] [P t(gly) 2] 2 (cis and trans)
+
6 Octahedral [MA 4B 2] [Co(NH 3) 4Cl2] 2 (cis and trans)
6 Octahedral [MA 2B 4] [Pt(NH 3)2Cl4] 2 (cis and trans)
6 Octahedral [MA 3B 3] [Cr(NH 3)3Cl3] 2 (facial and meridional)
+
6 Octahedral [MA 2B 2C 2] [Co(NH 3) 2 (H 2O) 2 Cl2] 5
7 Octahedral [MA 2(B-B) 2 ] [CoCl2 (en) 2]+ 2 (cis and trans)

M is the central metal. A, B, C and D are monodentate ligands. B–B represents a symmetrical bidentate
ligand like en. A–B represents an unsymmetrical biotentate ligand like gly (glycinate ion NH2–CH2–
COO–)
2. Optical isomerism in coordination compounds arises out of chirality in the coordination entity.
Optical isomers are mirror images that cannot be superimposed on one another. These are called
enantiomers or enantiomorphs. The two forms are called dextro (d) and laevo(l) depending upon the
direction in which they rotate the plane of polarised light in a polarimeter. Optical isomerism is common
in octahedral complexes (C.No = 6) having bidentate ligands.

C.NO Shape Type Example No. of optical is ome rs

3-
6 Octahedral [M(A-A) 3] [Co(en)3]3+ , [Cr(ox) 3] 2 (d and l )
+
Cis[CoCl2(en) 2] 2 (d and l )
6 Octahedral [MA 2 (B-B) 2]
trans [CoCl2(en) 2]
+ Nil

Bonding in coordination compounds

Many approaches have been put forward to explain the nature of bonding in coordination compounds.
eg. The Valence Bond Theory (VBT) and The Crystal Field Theory (CFT)
Valence bond theory: According to this theory, the metal atom or ion under the influence of the
ligands uses its (n–1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent hybrid
orbitals of definite geometry such as octahedral, tetrahedral, square planar etc. These hybridised
orbitals overlap with the ligand orbitals that can donate electron pairs for bonding.

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Orientation of hybrid
C.NO Type of hybridisation Example
orbitals in space
3
4 sp Tetrahedral [Ni(CO)4]

2 2-
4 dsp Square planar [Ni(CN)4]

3 2 3-
6 sp d Octahedral [FeF6]

2 3 3-
6 d sp Octahedral [Fe(CN)6]

3
5 dsp Trigonal bipyramidal [Fe(CO)5]

Crystal field theory:

This theory is an electrostatic model which considers the metal-ligand bond to be ionic arising purely
from electrostatic interactions between the metal ion and the ligand. Ligands are treated as point
charges in the case of anions or dipoles in the case of neutral molecules. The five d-orbitals in an
isolated metal atom/ion have the same energy ie they are degenerate. But when negative field due to
ligands (either anions or the negative ends of polar molecules like NH3 and H2O) in a complex surround
the metal atom/ion, the degeneracy of the d orbitals is lifted. It results in the splitting of d orbitals.
(crystal field splitting). The pattern of splitting depends upon the nature of the crystal field.
Magnetic properties and colour of coordination compounds.
Stability of coordination compounds
The stability of a complex in solution refers to the degree of association between the two species
(metal ion and ligands) involved in the equilibrium. The magnitude of the equilibrium constant (stability
constant or formation constant) for the association quantitatively expresses the stability of the complex.
Thus, for a reaction of the type:
M + 4L ML4
then the larger the stability constant, the higher is the proportion of ML4 that exists in the solution. Free
metal ions rarely exist in solution so that M will usually be surrounded by solvent molecules which will
compete with the ligand molecules L, and be replaced by them. We generally ignore these solvent
molecules for the sake of simplicity and write the four stability constants as follows.
[ML]
M+L ML K1 =
[M][L]
[ML 2 ]
ML + L ML2 K2 =
[ML][L]
[ML3 ]
ML2 + L ML3 K3 =
[ML2 ][L]
[ML 4 ]
ML3 + L ML4 K4 = [ML ][L]
3

where K1, K2, K3 and K4 are called stepwise stability constants or stepwise formation constants.
The overall stability constant or overall formation constant for the process M + 4L ML4 is
[ML 4 ]
4  . The stepwise and overall stability constants are therefore related as
[M][L]4
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4  K1  K 2  K 3  K 4
In general, n  K1  K 2  K 3  K 4 ...K n
The reciprocal of the overall formation constant of a complex is called the overall dissociation constant
or overall instability constant. Eg: The steps involved in the formation of the tetraammine copper (II)
ion from [Cu(H2O)4]2+ and NH3 are:
[Cu(H2O)4]2+ + NH3 [Cu(H2O)3(NH3)]2+ + H2O
[Cu(H 2 O)3  NH 3 ]2
 1 10 4
K1 =  Cu H O  2 [NH ]
  2 4  3

As concentration of H2O in the above aq. solution of Cu2+ remains essentially constant, it is ignored.
2 2
Cu(H 2 O)3  NH3    NH3 Cu(H 2 O) 2  NH3  2   H 2 O
2
 Cu  H 2 O 2  NH 3 2 
K2 = 2
 1103.2
Cu(H 2 O)3  NH3    NH3 

2 2
 Cu  H 2 O 2  NH 3 2   NH3  Cu  H 2 O  NH3 3   H 2O
2
Cu  H 2 O  NH3 3 
K3 = 2
 1102.7
Cu  H 2 O 2  NH 3  2   NH3 

2 2
 Cu  H 2 O  NH 3 3   NH 3  Cu  NH 3 4   H 2 O
2
 Cu  NH 3 4 
K4 = 2
 1 10 2
Cu  H 2O  NH 3 3   NH3 

The overall formation constant  4  for the process

2
 Cu  NH 3 4 
2
 Cu  H 2 O 4   4NH3  4H 2 O is
2
 Cu  NH3 4 
4  2
 K1  K 2  K 3  K 4  1 1011.9
Cu  H 2 O  4   NH 3 
4

Organometallic compounds
An organometallic compound is one in which the metal atom or ion is directly bonded to a carbon atom
of an organic group. Organometallics are of two types 1)  bonded organo metallics. eg. Grignard
reagents R–MgX, Frankland’s compound R2Zn 2)  bonded organometallics eg. dibenzene chromium,
Zeise’s salt, ferrocene etc.

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