VBT - Theory and Isomerism

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) Ionisation isomerism
c) Hydrate isomerism
d) Linkage isomerism
2. Stereoisomerism:
a) Geometrical isomerism
b) Optical isomerism
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 emperical 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
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.
Stereoisomers
Stereoisomers have the same atoms, same sets of bonds, but differ in the
relative orientation of these bonds.
Metal complexes that differ only in which ligands are adjacent to one another
(cis) or directly across from one another (trans) in the coordination sphere of
the metal are called geometrical isomers. They are most important for square
planar and octahedral complexes.
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.
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.
VALENCE BOND THEORY
Valence bond theory was introduced by Heitler and London (1927) and
developed further by Pauling and others.
It deals with :
 Electronic structure of central metal ion in its ground state
 Kind of bonding
 Geometry (shape)
 Magnetic properties of the complexes.
Assumptions:
The central metal atom or ion makes available a number of empty s, p and
d atomic orbitals equal to its coordination number.
These vacant orbitals hybridized together to form hybrid orbitals which are
the same in number as the atomic orbital hybridizing together.
All the hybrid orbitals are vacant, equivalent in energy and have definite
geometry.
The ligands have at least one σ-orbital containing a lone pair of electrons.
Vacant hybrid orbitals of the metal atom or ion overlap with the filled(containing lone
pair of electrons) σ-orbitals of the ligand to form ligand → metal σ-bond.
M→ L bond possesses a considerable amount of polarity because of the mode of its
formation
Important types of hybridization occurring in the first

row transition metal complexes
sp3 hybridization:
Tetrahedral molecules
sp3 : 4s, 4p3

dsp2 hybridization
Square planar molecule
Dsp2 : 3dx2-y2 , 4s, 4px, 4py

dsp3 hybridization
Trigonal bipyramidal Molecule.
dsp2 : 3dz2, 4s, 4p3,

sp3d2 hybridization
Octahedral Molecule
sp3d2 : 4s, 4p3 , 4dx2-y2 , 4dz2

d2sp3 hybridization
Octahedral Molecule
Dsp2 : 3dx2-y2 , 4dz2 , 4s, 4p3,

Inner Orbital Complexes
If the complex is formed by use of inner d-orbitals for hybridisation
(written as d2sp3) ,it us called inner orbital complex.
In the formation of inner orbital complex , the electrons of the metal are
forced to pair up and hence the complex will be either diamagnetic or will
have lesser number of unpaired electrons. Such complexes are Low Spin
Complexes.
Example, [Fe(CN)6]3- is inner orbital complex.
Outer Orbital Complexes

If the complex is formed by use of outer d-orbitals for hybridisation
(written as sp3d2) ,it is called as outer orbital complex.
Outer orbital complex will have larger number of unpaired electrons

since the configuration of the metal ion remains undisturbed. Such
complex is also called high spin complexes.
Example, [Fe(H2O)6]3+ is outer orbital complex.
µexp< µs for inner orbital octahedral complexes
Where as µexp ≈ µs for outer orbital octahedral complexes.
Where µexp = Experimental magnetic moment
and µs = Spin-only magnetic moment, which can be calculated by

the following equation:
µs = √(n(n+2) B.M
Question: Why all octahedral complexes of Ni2+ must be outer-orbital complexes?

Answer:
Question 2: The magnetic moment of [MnBr4]2- is 5.9 B.M. What is the
geometry of this complex ion?
Answer: coordination number = 4

It may be either square planar or tetrahedral geometry
Magnetic moment = 5.9

unpaired electrons n= 5 so
Hybridization will be sp3 hence geometry Td
↑ ↑ ↑ ↑ ↑ xx xx xx xx
3d5 4s 4p
Limitations of Valence Bond Theory
While the VB theory, to a larger extent, explains the formation, structures and
magnetic behavior of coordination compounds, it suffers from the following
shortcomings:
It involves a number of assumptions
It does not give quantitative interpretation of magnetic data
It does not explain the colour exhibited by coordination compounds.
It does not give a quantitative interpretation of the thermodynamic

or kinetic stabilities of coordination compounds.
It does not make exact predictions regarding the tetrahedral and square
planar structures of 4-coordinate complexes.
It does not distinguish between weak and strong ligands.

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ISOMERISM IN COORDINATION COMPOUNDS

Two principal types of isomerism are known among coordination

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

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

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

Important types of hybridization occurring in the first

sp3 : 4s, 4p3

Dsp2 : 3dx2-y2 , 4s, 4px, 4py

dsp2 : 3dz2, 4s, 4p3,

sp3d2 : 4s, 4p3 , 4dx2-y2 , 4dz2

Dsp2 : 3dx2-y2 , 4dz2 , 4s, 4p3,

Outer Orbital Complexes

Outer orbital complex will have larger number of unpaired electrons

Where as µexp ≈ µs for outer orbital octahedral complexes.

Where µexp = Experimental magnetic moment

and µs = Spin-only magnetic moment, which can be calculated by

Question: Why all octahedral complexes of Ni2+ must be outer-orbital complexes?

Answer: coordination number = 4

Magnetic moment = 5.9

Hybridization will be sp3 hence geometry Td

It involves a number of assumptions

It does not give quantitative interpretation of magnetic data

It does not explain the colour exhibited by coordination compounds.

It does not give a quantitative interpretation of the thermodynamic

It does not distinguish between weak and strong ligands.

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