# d-orbitals in complex ions for octahedral complex (Simple

explanation by crystal field theory)

* Crystal Field Theory (CFT)
This theory was developed by Bethe and Van Vleck and was
mainly applied to ionic crystals, which is called crystal field. This
theory has been proved to be successful in explaining
stereochemistry, reaction paths, magnetic properties, absorption
spectra, and thermodynamic properties of several complexes.

The following are the basic assumptions/postulates of CFT: 1.

Ligands are treated as point charges or point dipoles. 2. The
bonding between the metal cation and ligand is electrostatic
in origin. There is no interaction between metal orbital and
ligand orbital.
3. The d-orbitals on the metal have the same energy (degenerate).
However, when a complex is formed, the ligands destroy the
degeneracy of d-orbitals i.e., the orbitals now have different
energies.

The interaction between the electrons of cation and those of ligands

isresponsible for the splitting of the orbitals of the metal cation.
This splitting of five degenerate d-orbitals of the metal ion into two
sets of d-orbitals with different energies is called crystal field
splitting.
The two sets of d-orbitals i.e., dxy, dyz, and dxz commonly known as
t2g (triply degenerated) and dx2- y2and dz2, commonly known as eg
(doubly degenerated).
There occurs repulsion between electrons in metal d-orbitals and
electrons of ligands. Such repulsion is more when metal d-orbitals are
directed toward the ligands that when it is away from the ligand. Thus,
dx2- y2and dz2 orbitals that are directed towards the x, y, and z axes,
experience more repulsion, and energy is raised. The dxy, dyz, and dxz
orbitals that lie in between axes will be lowered in energy relative to
average energy in the crystal field.
The energy difference between eg and t2g set of orbitals is measured in
terms of parameter Δo or 10 Dq, known as Crystal Field Stabilization
Energy (CFSE). In an octahedral field, the eg orbitals are 0.6Δo (6Dq)
above the average energy level (baricentre) and t2g orbitals are 0.4Δo
(4Dq) below the baricentre. Hence, the total increase in energy of four eg
electrons is equal to the total decrease in energy of six t2g electrons,
preserving the centre of gravity.
# Reason for the colour of transition metal compounds
1. Incompletely filled d-shell (d-d transition)
 Transition metal complexes are mostly coloured due to the presence
of unpaired electrons or incomplete filling of d-orbitals where absorption
of light could lead to a d-d electronic transition from the visible region.

During the process of absorption of light, the electrons of transition metal

ions get excited from low energy d-level to high energy d-level. The
Colour of the companion ion can be explained with the help of CFT.
2. Polarisation
A cation polarizes the anions. It means, the cation distorts the
electron cloud and implies a greater covalent contribution. The
colour arises because of polarization. For example, the Ag+ion
polarizes the halide ions (Br –and I -). The AgBr is pale yellow and
AgI is yellow due to polarization.
3. By charge transfer
In the case of MnO4-, an electron is momentarily transferred from
oxygen to metal and momentarily changes O2-to O and reduces the
 oxidation state of metal from Mn7+ to Mn6+. Charge transfer
requires the energy levels of the two different atoms in a fairly
close state. Charge transfer always produces a very intense colour
like KMnO4 in solution is intensely purple.
# Catalytic Properties of Transition Metals
The main reasons for the catalytic activity of transition metals are
the ability to adopt multiple oxidation states and form complexes. In
other cases, the solid surface of transition metal provides surface area for
the formation of bonds between reactant molecules and atoms. This
increases the concentration of reactant molecules on the surface of the
catalyst and weakens the bond of the reactant.