10.

4 ligand Isomerism
If there is possibility of isomerism in the ligands themselves for example many organic ligands have such possi-
bilities, if complexes shows isomerism from this source then it is said to be ligand isomerism. For example
ligands, 1,2-diaminopropane(propylenediamine or pn) and 1,3-diaminopropane(trimethylenediamine or
tn) are such pairs. Similarly ortho-, meta- and para-toluidine (CH3C6H4NH2).
10.5 Polymerisation Isomerism
Considered to be a special case of coordination isomerism, in this the various isomers differ in formula weight
from one another, so not true isomers in real sense. For example [Co(NH3)4(NO2)2][Co(NH3)2(NO2)4],
[Co(NH 3) 6 ][Co(NO 2 ) 6], [Co(NH 3 ) 5(NO 2 )][Co(NH 3 ) 2 (NO 2 ) 4 ] 2, [Co(NH 3 ) 6 ][Co(NH 3 ) 2 (NO 2 ) 4 ] 3 ,
[Co(NH3)4(NO2)2]3[Co(NO2)6] and [Co(NH3)5(NO2)2]3[Co(NO2)6]2. These all have the empirical formula
Co(NH3)3(NO2)3, but they have formula weights that are 2,2,3,4,4 and 5 times this, respectively.
10.6 Geometric Isomerism & Optical isomerism
First we consider the cases of coordination number 4. The tetrahedral compounds can not show geometrical
isomerism as we all know that all four positions are equivalent in tetrahedral goemetry. So moving on to square
planar complexes there are different possibilities depending upon the formula of the compound. So we are
taking the different cases in sequence
(a) Square planar complexes with all monodentate ligands
In all following examples, we will be representing metal atom by symbol M, monodentate ligands
by small letters a, b, c, d, e, f ... etc and the symmetrical bidentate ligands are by AA, BB, CC etc
while the umsymmetrical bidentate ligands by AB, CD.. etc.
Formula No. of GI’s Trans pairs
Ma4 No GI (aa)(aa)
Ma3b No GI (aa)(ab)

Ma2b2 2 (aa)(bb) trans

(ab)(ab) cis

a b a b

Ma2 b2 M M

a b b a
Cis trans

The above compound is cisplatin used in cancer therapy.

Ma2bc 2 (aa)(bc) trans

(ab)(ac) cis

a b a c

Ma2bc M M

a c b a
Cis trans
 Coordination Compounds

Mabcd 3 (ab)(cd) aTb

(ac)(bd) aTc
(ad)(bc) aTd

a b a d

Mabcd M M

d c c b
aTc aTb

a b

c d
aTd

(b) Square planar complexes with one bidentate ligand and other two monodentate ligands
Complex No.of geometrical isomers Trans pairs

M(AA)a2 0 (Aa)(Aa)
M(AA)ab 0 (Aa)((Ab)
(Aa)(Ba)
M(AB)a2 0
(Aa)(Bb)
M(AB)ab 2 (Ab)(Ba)

A a A b

M M

B b B
a
(c) Square planar complexes with two bidentate ligands
Complex No.of geometrical isomers Trans pairs

M(AA)2 0 (AA)(AA)

M(AB)2 2 (AB)(AB)
(AA)(BB)
A A A B

M(AB)(AB) M M

B B B A

M(AA)(BB) 0 (AB)(AB)
M(AA)(CD) 0 (AC)(AD)
M(AB)(CD) 2 (AC)(BD)
(AD)(BC)

A C A D

M(AB)(CD) M M

B D B C
ATD ATC
JEE-Chemistr y
CN = 6 (Octahedral Complexes)
Again the different cases possible are
Complexes containing only mondentate ligands
Total possible formula can be

i Ma 6 
 no.G.I  only one form is possible  ( both will be optically inactive)
 ii  Ma 5 b 
(iii) Ma 2 b 4 – 2 (aa)(bb)(bb) (optically inactive)
(ab)(ab)(bb) (optically inactive)

b b a
b a b a b b

Ma2b4 M M M

|||
b a a b b b
b b a

both a are in cis both a are in trans

(iv) Ma4bc – 2 (aa)(aa)(bc) (optically inactive)
(aa)(ab)(ac) (optically inactive)

a c b
a b a b a a

M M
|||

Ma4bc M

a c a a a a

a a c

Cis Trans

(v) Ma3b3 – 2 (aa)(ab)(bb) (optically inactive)

(ab)(ab)(ab) (optically inactive) Ma3b3

b b

a b a b

M M

a a a
b

a b

facial or fac- Meridional or Mer-

2 triangular faces
such that each
corner is occupied
by similar ligands
 Coordination Compounds
Like [Co(NO2)3(NH3)3]. If each trio of donor atoms occupy adjacent positions at the corners of an octahedral
face, we havethe facial (fac) isomer. When the positions are around the meridian of the octahedron we, get the
meridional (mer) isomer
b b
a b b a

M M

a b a a

a b
Fac- (a) Mer-

NH3 NH3
O2N NH3 H2N NO2

Co Co

O2N NH3 O2N NO2

NO2 NO2
Fac- Mer-
(b)

(vi) Ma3b2c – 3
The trans pairs for the three isomers are
(aa)(ab)(bc) (optically inactive)
(aa)(bb)(ac) (optically inactive)
(ab)(ab)(ac) (optically inactive)

(vii) Ma3bcd – 4
The trans pais for the four possible isomers are
(aa)(ab)(cd) (optically inactive)
(aa)(ac)(bd) (optically inactive)
(aa)(ad)(bc) (optically inactive)
(ab)(ac)(ad)

(viii) Ma2b2c2 – 5
The trans pairs for the possible isomers are
(aa)(bb)(cc) (optically inactive)
(aa)(bc)(bc) (optically inactive)
(bb)(ac)(ac) (optically inactive)
(cc)(ab)(ab) (optically inactive)
(ab)(ac)(bc) (optically active)

(ix) Ma2b2cd – 6

(x) Ma2bcde – 9

(xi) Mabcdef – 15
JEE-Chemistr y
(II) Compounds containing bidentate ligand
a
a A

[M(AA)a4] – 1 form possible (No G.I.) M

a A

b a
A a A a

M(AA)a3b – 2 M M

A a A b

b a
bTa aTa

a a b
A b A a A

M(AA)a2b2 – 3
M M M

A b A b A

a b b
aTa aTb bTb

M(AA)abcd – 6
M(AA)3 – 1 form (No G.I.)
MI(AB)3 – 2 form

A
A A
A
A B
M
Fac. Mer. M
B B
B B
B
B

A Coordination compound which can rotate the plane of polarised light is said to be optically active.
When the coordination compounds have same formula but differ in their ability to rotate directions of
the plane of polarised light are said to exhibit optical isomerism and the molecules are optical isomers.
The optical isomers are pair of molecules which are non-super impossible mirror images of each
other. This is due to the absence of elements of symmetry in the complex.
Optical isomerism is expected in tetrahedral complexes of the type Mabcd
Optical isomerism is not in squareplanar complexes on account of the presence of axis of
symmetr y.
 Coordination Compounds
Optical isomerism is very common in octahedral complexes.
(a) [Ma2B2C 2]n± Out of five different geometrical isomers, only one is optically active [Pt(py)2(NH 3)2Cl2]2+
py py
2+ 2+
Cl Py py Cl

Pt Pt

Cl NH3 H3N Cl
NH3 NH3
Cis-d-isomer Mirror Cis-l-isomer

(b ) [Mabcdef] All 15 different geometrical isomers are optically active

[Pt(py)NH3NO2ClBrI]

py py
py NO2 O2N py

Pt Pt

Cl NH3 H3N Cl
I I
d-isomer Mirror l-isomer
n±
( c ) [M(AA)3] [Co(en)3]3+
3+ 3+
en en
en

Co Co

en
en en
d-form Mirror l-form

(d ) [M(AA)2a2]n± [Co(en)2Cl2]+
3+
en en 3+
Cl Cl

Co Co

Cl Cl
en en
Cis-d-form Cis-l-form
Mirror
Trans form of [M(AA)2a2]n± does not show optical isomerism
JEE-Chemistr y

(e) [M(AA)2ab]n± (Co(en)2NH3Cl]2+

en 2+ en 2+
Cl Cl

Co Co

H3N NH3
en en
Cis-d-form Cis-l-form
Mirror
(f) [M(AA)a2b2] [CrCl2(en)(NH3)2]+

N en + en N +
H3N N N NH3
Cr Cr
H3N Cl Cl NH3
Cl Cl

(g) [M(AB)3] (Cr(gly)3]

gly gly

Cr gly Cr
gly

gly gly
Cis or trans-d-form Cis or trans-l-form
Mirror

 ISOMERISM IN COMPLEXES
(a) Compounds which have the same molecular formula, but differ in their properties due to the difference in
structure are called as Isomers.
(b) Isomerism is commonly considered, to be the characteristic of only organic compounds, it is also found
although less frequently among inorganic substances.
Classification of isomerism

Type of isomerism

Structural isomerism Stereo isomerism

Ionization Hydrate Coordination Linkage Ligand Geometrical Optical

Coordination
position
 Coordination Compounds

Note : General formula Total No. of geometrical isomers

Mabcdef 15

Ma2bcde 9

Ma2b2cd 6

Ma2b2c2 5

Ma3bcd 4

Ma3b2c 3

Ma3b3 2

Ma4bc 2

Ma4b2 2

Ma5b Nil

Ma6 Nil

Here M = central atom. a, b, c, d, e, f = Monodentate ligands

NUMBER OF POSSIBLE ISOMERS FOR SPECIFIC COMPLEXES
Formula Number of stereoisomers Pairs of Enantiomers
Ma2b2 2 0
Ma3b3 2 0
Ma4bc 2 0
Ma3bcd 5 1
Ma2bcde 15 6
Mabcdef 30 15
Ma2b2c2 6 1
Ma2b2cd 8 2
Ma3b2c 3 0
M(AA)(BC)de 10 5
M(AB)(AB)cd 11 5
M(AB)(CD)ef 20 10
M(AB)3 4 2

1. Which of the following is a pair of ionization isomers

(A) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
(B) [Cr(H2O)5Cl]Cl2.H2O and [Cr(H2O)4.Cl2]Cl.2H2O
(C) [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(D) cis-[Pt(NH3)2Cl2] and trans-[Pt(NH3)2Cl2]
2. In coordination compounds, the hydrate isomers differ :-
(A) In the number of water molecules of hydration only
(B) In the number of water molecules only present as ligands
(C) Both in (A) and (B)
(D) In their coordination number of the metal atom