Co-ordination Compounds

Module 24.3: Isomerism

Two or more molecules having the same molecular formula but different
structural or spatial arrangement are called isomers.
They are of two types.

a. Structural isomerism
b. Stereo isomerism

Stereo isomerism in complex compounds:

Two or more complexes having same molecular composition but different

arrangement of atoms (or) groups in space is called as stereoisomerism.

It is of two types.

a. Geometrical isomerism
b. Optical isomerism

Geometrical isomerism in co-ordination number 6 compounds:

The arrangement of six ligands in a complex around the central metal ion is
possible in two different ways. Those are regular hexagon and regular
octahedron.

1 L
6 2 L L
M M
5 3 L L
4
Hexag L
Octahed
on ron
If the complex Ma4b2 (where M = central metal atom; a,b = ligands) has hexagonal
structure it can give three isomers corresponding to (1, 2), (1, 3) and (1, 4)
positions of a and b, while octahedral arrangement can give only two isomers. X –
ray analysis confirmed that co-ordination number 6 complexes exhibit octahedral
arrangement by giving two isomers of Ma 4b2 type. Hence co-ordination number 6
complexes have octahedral structure.

1. No isomerism is possible in [Ma6] or Ma5b of complexes

Example: [Co(NH3)6]3+; [Co(NH3)5Cl]2+

2. [Ma4b2] and [Ma4bc] type of complexes can give two isomers. Those are cis
and trans – isomers.

Example: [Co(NH3)4Cl2]+ gives cis and trans isomers.

Cl + Cl- +
H3 - Cl -
H3 N
N Co+ N Co H3
3 +3
H3 NH H3 NH
N NH N Cl -
3 3
Cis
3 Tra
ns

3. [Ma3b3] type of complexes can exhibit geometrical isomerism.

Example: [Co(NH3)3Cl3] gives Cis – trans isomers.

 C NH
H3 l C C C
3
N C l l C l
H3 o C H3 o C
N NH l NH l
N
Cis
3
Tra
3
ns

4. [M(aa)2b2] (where aa = bidentate ligand) type of complexes having two

bidentate ligands, can exhibit geometrical isomerism.

Example: [Co(en)2Cl2]+ gives cis and trans isomers.

C + C +
l C l
e C l e C e
n o n o n
e C
Cis n l
Tra
ns

Optical isomerism in co-ordination number 6 compounds::

1. The cis isomer of [M(aa)2b2] type complexes has no plane of symmetry. So it

can give two isomers (d and l)
 C + C +
l C C l
e C l l C e
n o o n
e C
d- e l
n
form n

2. Complexes of [M(aa)3] type having three bidentate ligands are also

unsymmetrical and gives optical isomerism.

Example: [Pt(en)3]4+ gives optical isomers.

e e
n 4 n 4
+ +
e P P e
n t t n
e e
d– n l– n
form form

Stereo isomerism in co-ordination numbers 4 compounds:

Complex compounds with co-ordination number 4 give either tetrahedral or

square planar structure.

1. No isomers are possible [Ma4], [Ma3b] types complexes (square planar or

tetrahedral)

Example: Ni(CO)4, [Cu(NH3)4]2+

2. [Ma2b2] and [Ma2bc] complexes of some metals like Pt (II), Pd (II), Ni (II), Cu (II)
give square planar structure having dsp2 hybridization.
 Example: [Pt(NH3)2(CN)2] gives cis, trans isomers

H3 C H3 C
N N N N
P P
t t
H3 C N NH
Cis N Trans
N C 3

The geometrical isomers of [Pt(NH3)2Cl2] are

H3 Cl H3 Cl
N P N P
H3 t Cl t NH
C
N Cis – l Trans – 3
isomer isomer

Some complex compounds of Cu, Zn, Ni can give tetrahedral structure. These
metals undergo sp3 hybridisation

[Mabcd] type of complex gives optical isomerism, if it has tetrahedral structure.

a a

M d
M
a d b
c c
Three geometrical isomers are possible, if they have square planar structures.
 a b a c a b
M M M
d c d b c d
Example: [Pt(NH3)(Py)ClBr] gives three isomers.

Assignment Questions:

1. Draw the structures of optical isomers of

a. [Pt(en)3]4+
b. [Co(en)2Cl2]+

Example Set:

1. Which one of the following square planar complexes will show cis – trans
isomerism
a. Ma4
b. Ma3b
c. Ma2b2
d. Mabcd

Solution: c)

2. The number of isomers possible for square planar complex K2[PdClBr2(SCN)]

a. 2
b. 4
c. 5
d. 6

Solution: a)

3. Write an account on geometrical isomerism in complexes giving examples.

Solution:

Geometrical isomerism in co-ordination number 6 compounds:

The arrangement of six ligands in a complex around central metal ion is possible
in two different ways. Those are regular hexagon and regular octahedron.

1 L
6 2 L L
M M
5 3 L L
4
Hexag L
Octahed
on ron

If the complex Ma4b2 (where M = central metal atom; a = ligand) has hexagonal
structure it can give three isomers corresponding to (1, 2), (1, 3) and (1, 4)
positions of a and b, while octahedral arrangement can give only two isomers. X –
ray analysis confirmed that co-ordination number 6 complexes exhibit octahedral
arrangement by giving two isomers of Ma4b2 type. Hence co-ordination number 6
complexes have octahedral structure.

1. No isomerism is possible in [Ma6] or Ma5b of complexes

Example: [Co(NH3)6]3+; [Co(NH3)5Cl]2+

2. [Ma4b2] and [Ma4bc] type complexes can give two isomers. Those are cis and
trans – isomers.

Example: [Co(NH3)4Cl2]+ gives cis and trans isomers.

Cl + Cl- +
H3 - Cl- H3 N
N Co+ N Co H3
3 +3
H3 NH H3 NH
N NH N Cl -
3 3
Cis
3 Tra
ns
3. [Ma3b3] type of complexes can exhibit geometrical isomerism.

Example: [Co(NH3)3Cl3] gives cis – trans isomers.

C NH
H3 l C C C
3
N C l l C l
H3 o C H3 o C
N NH l NH l
N
Cis
3
Tra
3
ns

Problem Set:

1. Geometrical isomerism would be expected from?

a. [Zn(NH3)2(H2O)2]2+
b. [Cu(CN)4]3-
c. [Pt(NH3)2Cl2]
d. [Ag(NH3)2]+

Solution: c)

2. Which of the following octahedral complexes does not show geometrical

isomerism (a and b are monodentate ligands)?
a. Ma3b3
b. Ma4b2
c. Ma5b
d. Ma2b4

Solution: c)

3. Draw structures of the geometrical isomers of [Fe(NH3)2(CN)4].

Solution:

N N
N N - N C -
H3 H
C F H C F3 N
N e C3 N e C
C N
C CN N C Tr N
H3
is a
ns

Exercise Questions:

1. Why is geometrical isomerism not possible in tetrahedral complexes having

two different types of unidentate ligands?
2. Give evidence that [Co(NH3)5Cl)SO4 and [Co(NH3)5SO4]Cl are ionization
isomers?
3. Platinum (II) forms square planar complexes and platinum (IV) forms
octahedral complexes. How many geometrical isomers are possible for each of
the following complexes? Draw their structures.
a. [Pt(NH3)3Cl]+
b. [Pt(NH3)Cl5]-
c. [Pt(NH3)2Cl(NO2)]
d. [Pt(NH3)4ClBr]+2

Solutions to Exercise Questions:

1. b
2. Tetrahedral complexes do not show geometrical isomerism because the relative
positions of the unidentate ligands attached to the central metal atom are the
same w.r.t each other.

3.
a. A pair of optical isomers
 NH NH
O2 3
N H3 3 N
N H3 N O2
C C
o o
H3 NH H3 N
N N 3 N NH H3
H3 3

It can also show linkage isomerism

[Co(NH3)5(NO2)](NO3)2 and [Co(NH3)5(ONO)](NO3)2

It can also show ionization isomerism

[Co(NH3)5(NO2)](NO3)2 and [Co(NH3)5](NO3)](NO2)(NO3)

b. Geometrical (cis-, trans-) isomers of [Pt(NH3)(H2O)Cl2] can exist

C N H C
l P H 3 P l
C t H
3 NC t H
C Tr
l 2 l 2
i a
s O n O
s
4.
a. No isomers are possible for a square planar complex of the type Ma 3b. It is
[Ma3b] type of a complex
 +
Cl NH
P 3

t
H3 NH
N 3

b. No isomers are possible for an octahedral complex of the type Mab 5. This is
a complex of the type Ma5b or Mab5
NH3 _
Cl C
l
Pt
C C
l Cl l

c. cis and trans isomers are possible for a square planar complex of the type
Ma2bc
Cl N Cl N
H3 H3
P P
O2 t N t
H3 NO
Ci Tra
N H3 N 2
s ns

d. cis and trans isomers are possible for an octahedral complex of the type
Ma4bc
 NH C
H3 C H3 l N
3
N P l N P H3
H3 t B H3 t N
N NH r N B H3
Ci Tr
r
s3 an
s

5. A, B and C are three complexes of chromium (III) with the empirical formula
H12O6Cl3Cr. All the three complexes have water and chloride ion as ligands.
Complex A does not react with concentrated H 2SO4, whereas complexes B and
C lose 6.75% and 13.5% of their original mass, respectively , on treatment with
concentrated H2SO4 identify A , B and C.

Solution:

The compound A does not react with concentrated H 2SO4 implying that all water
molecules are coordinated with Cr3+ ion. Hence, its structure would be [Cr
(H2O)6]Cl3. The compound B loses 6.75% of its original mass when treated with
concentrated H2SO4. This loss is due to the removal of water molecules which
is/are not directly coordinated to Cr3+ ion.

The mass of water molecules removed per mole of the complex

= X molar mass of the complex

= X 266.5 g = 17.98 g (one mole H2O)

Compound B will be [Cr(H2O)5Cl](H2O)Cl2
The compound C loses 13.5 % of its mass when treated with concentrated
H2SO4 which is twice of the mass lost by the compound B. Hence compound
C will be [Cr (H2O)4Cl2] (H2O)2Cl.
7. The acidic, aqueous solution of ferrous ion forms a brown complex in the
presence of , by the following two steps. Complete and balance the
equations.
[Fe (H2O)6]2+ + + H+ …… + [Fe(H2O)6]3+ + H2O
[Fe(H2O)6]2+ + …… ……+ H2O

Solution:

3[Fe (H2O)6]2+ + + 4H+ NO + 3[Fe(H2O6)]3+ + 2H2O

[Fe (H2O)6]2+ + NO [Fe(H2O)5 NO]2+ + H2O

8. Write the chemical reaction associated with the brown ring test.

Solution:

NaNO3 + H2SO4 NaHSO4 + HNO3

6 FeSO4 + 2HNO3 + 3 H2SO4 3 Fe2(SO4)3 + 4 H2O + 2 NO
[Fe(H2O)6]SO4.H2O + NO [Fe(H2O)5 NO] SO4 + 2 H2O
(brown ring)

9. Nickel chloride, when treated with dimethyl gyloxime in presence of

ammonium hydroxide, a bright red precipitate is obtained. Answer the
following.
a) Draw the structure of the complex showing H- bonds
b) Give oxidation state of nickel and its hybridization
c) Predict the magnetic behavior of the complex.

Solution:

(a)
O H–O

H3C – C = N N = C – CH3

Ni

H3C – C = N N = C – CH3

O–H O
 Bis(dimethylglyoximato) nickel (II).

(b) Charge on Ni in the complex is +2 and it is dsp2 hybridized.

(c) Since number of unpaired electrons in Ni 2+ is zero, the complex is
diamagnetic.

10. Fe3+ (A) (B)

Blood red Colorless
Coloration

What are (A) and (B)? Give IUPAC Name of (A). Find the spin only
magnetic moment of (B).
Solution:
Fe3+ + SCN− [Fe (SCN)(H2O)5]2+
(excess) (A)(blood red)

[Fe (SCN)(H2O)5]2+ + 6F− [FeF6]3- + SCN-

IUPAC name of A is pentaaquathiocyanato ferrate (III) ion
IUPAC name of B is hexafluoroferrate (III)
In [FeF6]3- co-ordination [Link] Fe = 6
In [FeF6]3- oxidation state of Fe = +3
It has 3 unpaired electrons, n = 5
Magnetic moment = = 5.92 B.M.

11.(Colourless liquid) MCl4 Purple color compound ; M = Transition

metal
MCl4 (B)
White fumes
Identify (A), (B) and MCl4. Explain color difference between MCl4 and (A).
 Solution:

(A) [Ti(H2O)6]Cl3 (B) HCl

TiCl4 TiCl3 [Ti(H2O)6]Cl3

Purple (A)

TiCl4 + (n + 2) H2O TiO2 (H2O)n + 4 HCl ↑

White fumes
4+ 0 3+ 1
(B) Ti = [Ar] 3d ; Ti = [Ar]3d

TiCl4 is colorless since Ti4+ has no d electrons. Hence d-d transition is impossible.
On the other hand, Ti3+ is colored due to d-d transition. Ti3+ absorbs greenish
yellow compound of white light, hence its aqueous solution is purple which is
complementary color of greenish yellow in white light.

12. The number of water molecules (s) directly bonded to the metal centre in
CuSO4.5H2O is
Solution:
The number of water molecules directly bonding to the metal centre in
CuSO4.5H2O is 4

H2O
OH2
Cu2+
.H2O
H2O OH2

[Link] number of geometrical isomers for the complex [RhCl(CO)(PPh3)

(NH3)] is
Solution:
Four different ligands and hence three different arrangements.