The octahedral arrangement of six ligands surrounding the central metal ion is as

shown in the figure.

fig 10.4 - Octahedral arrangement of six ligands surrounding the central metal ion
Looking at the figure, we observe that as the ligands approach the x,y and z axis, the
two d-orbitals lying along the axis namely dx2 - y2 and dz2 will suffer more electrostatic
repulsions and hence their energy will be greater than the other three d-orbitals d xy, dyz
and dzx,
Accordingly, the d-orbitals will thus split as follows.

fig 10.5

Inner and outer orbital complexes are compounds or ions that have ligand bonding associated
with s, p, and d orbitals all at the same time. This comes from the older theory called "valence-
bond" theory. The complexes primarily involve transition metals and the orbitals that form are
called hybrid orbitals such as d2sp3, or sp3d2 depending on whether the complex is an inner or
outer orbital type.

Inner orbital complexes involve lower lying d-orbitals then s and p orbitals such as d2sp3 in
[Co(NH3)6]^3+ or [Fe(CN)6]^4-.
Outer orbital complexes involve the use of the s- and p-orbitals of one energy level and the d-
orbitals on the same energy level. An example is [Fe(H2O)]^2+ in which Fe^2+ uses the 4s, 4p,
and 4d orbitals to bind the six water molecules to the Fe^2+ ion.

Remember, this is a picture we get from valence-bond theory. The ligands that form inner orbital
complexes tend to be weak field ligands, while those that form outer orbital complexes tend to be
strong field ligands. The spectrochemical series gives an order of ligands from strong field to
weak field in the 2nd link below.

A theory similar to molecular orbital theory which is concerned with the formation of

covalent bonds. It uses "outer orbital" and "inner orbital" hybridization to

explain the formation of compounds.

Outer orbital hybridization (also called high spin) see the and orbitals, so only

the , , and orbitals are available.