Coordination Chemistry:

Part -1

Prepared by
Dr. Chanchal Haldar
& Dr. R P John
Indian Institute of Technology (ISM) Dhanbad
•Recommended Books
• Shriver Atkins Inorganic Chemistry byAtkins, Overton,
Rourkee, Weller and Armstrong, Oxford Univ. Press, 4th Ed, 2009.

•Inorganic Chemistry: Principle, structure and reactivity, by J.

E. Huheey, E. A. Keiter and R. L. Keiter, Harper Collins, 4th Ed,
1993.
•Principles of Inorganic Chemistry by Pri, Sharma and Kalia,
Milestone publishers
•Basic Inorganic Chemistry, J. D. Lee, Wiley Blackwell, 2008
What is a Transition Metal?
 Color of transition metal complexes

Sapphire: Al2O3 with and Impurity

titanium and iron impurities are
present together, and in the
correct valence states, the result is a
deep-blue color. Fe2+ and Ti4+ ions
are substituted for Al3+

Ruby : Al2O3 With

Impurity of Chromium

Emerald is a gemstone and a variety of the mineral beryl (Be3Al2(SiO3)6)

colored green by trace amounts of chromium and sometimes vanadium
Naturally Occurring Coordination Compounds
 Coordination Compounds
 A central metal atom or ion to which ligands are bound by coordinate
covalent bonds
Given a problem, how will
you identify type and no.
of isomers a molecule
may possess?

7
ISOMERISM IN COORDINATION COMPOUNDS

Two or more different compounds having the same formula are called
isomers.

Two principal types of isomerism are known among coordination

compounds. Each of which can be further subdivided.

1. Structural Isomerism
a) Coordination isomerism
b) Ionization isomerism
c) Hydrate isomerism
d) Linkage isomerism

2. Stereoisomerism:
a) Geometrical isomerism
b) Optical isomerism

8
 Structural Isomers

a) Coordination isomerism:
where compounds containing complex anionic and cationic parts can be
thought of as occurring by interchange of some ligands from the cationic
part to the anionic part.

One isomer [Co(NH3)6] [Cr(C2O4)3]

another isomer [Co(C2O4)3] [Cr(NH3)6]

b) Ionization isomers:
Complexes which have the same empirical formula but give different ions in
solution on ionization are called ionization isomers.

one isomer [PtBr(NH3)3]NO2 -> NO2- anions in solution

another isomer [Pt(NO2)(NH3)3]Br -> Br- anions in solution

9
 c) Hydrate isomerism:
Hydrate (solvent) isomerism occurs when water (or another solvent) can
appear within the primary or secondary coordination sphere of a metal ion
The best known example of this occurs for chromium chloride
"CrCl3.6H2O" which may contain 4, 5, or 6 coordinated water molecules.

d) Linkage isomerism:
Occurs with ambidentate ligands. These ligands are capable of
coordinating in more than one way. The best known cases involve the
monodentate ligands SCN- / NCS- and NO2- / ONO-.

[Co(ONO)(NH3)5]Cl nitrito isomer -O attached

[Co(NO2)(NH3)5]Cl nitro isomer - N attached.
10
Linkage Isomers

11
 Stereoisomers
Stereoisomers have the same atoms, same sets of bonds, but differ in the
relative orientation of these bonds.

12
13
Octahedral:
Compound type No. of isomers
Ma4b2 2 (cis- and trans-)
Ma3b3 2 (fac- and mer-)
MAA2b2 3 (2*cis- and 1 trans-)
here a, and b, represent monodentate ligands and AA is a bidentate ligand.

14
Problem:
Draw and label all possible isomeric structures of the following compound type

Compound type No. of isomers

1) Ma6 01
2) Ma5b 01
3) Ma4b2 02
4) Ma3b3 02
5) Ma3b2c 03
6) Ma3bcd 04(stereoisomers)
here a, b, c and d, represent monodentate ligands

1) Ma6 2) Ma5b
3) Ma4b2

4) Ma3b3
4) Ma3b2c

5) Ma3bcd
Optical Isomers:
Optical isomers are related as non-superimposable mirror images and differ in the
direction with which they rotate plane-polarised light. These isomers are referred to as
enantiomers or enantiomorphs of each other and their non-superimposable structures
are described as being asymmetric.

18
19
Optically active square planar complex:
Diastereomers

Achiral molecules
Chiral

21
 Exercises
• Identify the number and type of isomers for the compounds
with the following molecular formula.
• [Pt(NCS)NH3)3]+, Co(NH3)5BrSO4, FeCl2 .6H2O, Cr(NO2)2 .6H2O,
[Co(Br)2Cl(H2O)], [CoBr(NO2)(NH3)(H2O)], Pd(Gly)2,
PdBrCl(NH3)2, [Co(en)3]2+, Ir(Cl)3(NH3)3, [Co(Cl)(en)(NH3)2]+
• Which of the following complexes are chiral?
[Cr(ox)3]3-, cis-[Pt(Cl)2(en)], cis-[Rh(Cl)2(NH3)4]+, fac-
[Co(NO2)3(dien), mer-[Co(NO2)3(dien)
{dien = diethylenetriammine}

22