Isomers of

Coordination Complexes

Coordination Chemistry

1 24.2 Isomers of Coordination Complexes 12.2.00 12:06 AM

 Geometry
Coordinate Number (CN):
Number of donor atoms bonded to metal
2- Coordinate - linear
4 - Coordinate tetrahedral and sq planar
ML4 , Pt(II) is always CN = 4
6- Octahedral
ML6, Cr(III) and Co(III) CN = 6

CN influence by
size of metal ion
surrounding ligand
Small metal /large ligand - Low coordinate number
Large metal / small ligand - High coordination number
i.e., FeF63- and FeCl4- only
2 24.2 Isomers of Coordination Complexes 12.2.00 12:06 AM
 Historic Perspective
During early / mid 1800’s bonding was not well understood. Most
widely accepted theory on bonding was the chain theory supported
by Sophus Jorgensen (1837 - 1914). The structure of Co(NH 3)6Cl3
was explained in the classrooms using this theory in the late 1800’s.
In 1890 Alfred Werner proposed a new bonding scheme and wrote a
paper called “coordination theory”. In 1913 Werner won the 14th
Noble Prize for his work.

3 24.2 Isomers of Coordination Complexes 12.2.00 12:06 AM

 Isomers -
Same formula different properties. i.e., N2O  NNO or NON
Structural isomer
Compd with different atomic bond connectivity.
Coordination sphere isomer Linkage isomer
Stereoisomer
Same atomic connectivity but different arrangement.
Geometrical isomer Optical isomer

4 24.2 Isomers of Coordination Complexes 12.2.00 12:06 AM

 Structural isomer-
Different Atomic connectivity
Coordinate sphere isomer - Complexes in which the
ligand is bonded differently to the metal.
Co 3Cl 6H2O
H
O H
H H
O
H H
H

O H
H
O H
O
O O
H
H
H H
O
H Co
H

Cl3 Cl2•H2O
O Co H
H
O Co H
H
O

O
H Cl • 2H2O
Cl
O Cl
H H

H
O
H
O
H
H H
Cl
H
H

i) six H2O in ii) five H2O and one iii) four H2O and two
coordination Cl in coordination Cl in coordination
sphere. sphere. sphere.
Violet Dark Green Green
5 24.2 Isomers of Coordination Complexes 12.2.00 12:06 AM
 Linkage Isomers
Linkage isomer - Isomer complexes in which the
ligand coordinates to the metal by different donor
atoms. i.e., Nitrite ion, NO2-

Nitro ligand as an N-donor Nitrito ligand as an O-donor

Other ligand capable of switching donor atom

SCN-, CN-, 2.2’-bipyridine
6 24.2 Isomers of Coordination Complexes 12.2.00 12:06 AM
 Linkage Isomer of 2,2’-bipyridine

Two compounds formed by the linkage isomer of

bpy is shown. Small changes in ligand bonding
could result in dramatic chemical property change.

C
Carbon C C Nitrogen
C

C
C Bonded C
C
bonded
C
C C
C C C

C C

N C N C
N N
C C
C C C
C
C C C C

Ir C Ir N
C N C C N C

C N C C
C C
C C
N N
N C N C
C C
C C C C
C C
C C
C C C
C C
C C
C

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 Geometric Stereoisomer
Geometric isomer - Compounds with similar atomic
connectivity but different atomic arrangement in space.
Diaminedichloroplatinum(II)

Cisplatin transplatin
Diaminecisdichloroplatinum(II) diaminetransdichloroplatinum(II)

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 Mirror Image
Mirror images cannot be exactly superimposed over each other.
Complexes which form mirror images are called chiral

Most of the human body

is chiral (the hands).
Enzymes are the most
highly chiral substances
known.

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 Optical Isomers
Optical isomer - Isomer complex in which the
atomic connection are the same but arrangement is such
that the two complexes are not superimposable.

Optical isomers are called enantiomer.

Chiral Complexes are also called enatiomers

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 Optical Inorganic Isomers

Enantiomer - Isomer that are mirror image to each

other.
Handedness:

“R” “S”

Molecules/Ions that have enantiomer are chiral

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 Optical Isomer and Interaction with Light
Enatiomers rotate the plane of polarized light.

Dextrorotatory- “d” isomer

Complex which rotates plane of polarized light to the
right.
Levorotatory- “l” isomer
Complex which rotates plane of polarized light to the
left.
Chiral molecules are optically active because effect on light.
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