THEORIES OF COORDINATION COMPOUNDS

Crystal Field Theory

In the crystal field theory the following assumptions are made.

(1) This theory considers a complex as a combination of a central ion surrounded by other
ions or molecules with electrical dipoles called ligands. It regards these ligands as point
charges or as point dipoles.
(2) The bonding between the metal cation and ligands arises due to the electrostatic
attraction between the nucleus of the metal cation and the partial negative charge
invariably present on the ligands. Thus the bond between the metal and the ligand is
purely ionic
(3) The interaction between the electrons of the cation and those of the ligands is entirely
repulsive. These repulsive forces are responsible for the splitting of the d orbitals of the
metal cation.
(4) In its simplest form, the crystal field theory does not consider the overlapping between
the metal orbitals and ligand orbitals.
(5) The d orbitals which are degenerate (of equal energy) in a free metal ion have their
degeneracy destroyed by the approach of the ligands during the formation of a complex.
Crystal Field Splitting of d Orbitals
in Different Geometries
Let us consider an octahedral complex, ML6, where M
is a metal ion and L stands for a ligand.Here four
ligands lie in one plane and the other two in a plane
perpendicular to the first plane.
Six ligands are at the corners of a regular octahedron
and they all lie along the three perpendicular axes, x, y
and z. Thus we see that all those orbitals which lie in
the direction of these axes will experience a stronger
force of repulsion as compared to the orbitals which lie
between the axes
So the orbitals which lie along the axes will be repelled
more by the ligands and will be higher in energy than
dxy, dyz and dxz set of orbitals.
Sp3
Dia