Molecular Orbital of Octahedral Complex

• The molecular orbitals we are seeking will be linear combinations of metal and ligand atomic orbitals having the
same symmetry, it is appropriate to begin by constructing linear combinations of the ligand orbitals , or ligands
group orbitals (LGOs), that will overlap with metal orbitals along the octahedral bonding axes.
• The LGOs must match the symmetries of the metal orbitals available for bonding. As has already been stated,
the metal valence orbitals of interest are the ns, np and (n-1)d. their symmetry properties is an octahedral
complex can be determined by reference to an Oh character , which reveals that the s orbital transforms as a 1g
and the set of p orbitals as t1u, where as the five d orbitals lose their degeneracy to form e g (dz2 and dx2- y2) and t2g
(dxy, dxz and dyz) sets .
• In order to actually participate in a σ-bond within the complex, a metal orbitals must be capable of positive
overlap with the ligand group orbital directed along the bonding axes .
• The a1g metal orbital will be spherical, therefore being capable of overlapping with LGOs on all axes.

• The t1u an eg sets all have lobes concentrated along the bond directions and thus also are capable of bond
participation. This shown in fig. 1(e) for the d x2-y2 orbital.

• The t2g set, however, will have lobes directed between the bonding axes and thus will yield no net overlap with
ligand orbitals fig. 1(e)
 fig.1(a) fig.1 (b) fig.1(c) fig.1(d)
Ligand group orbital of fig.1(a) s orbitals; fig.1(b), (c) and (d) p orbitals; fig.1(e) d orbitals fig.1(e)

fig. 2

σ-bond molecular orbital diagram for a complex octahedral symmetry

From the above diagram the metal t2g orbitals cannot participate in sigma overlap, considered nonbonding
molecular orbital in complexes where there is no possibility for bonding
The a1g and t2u molecular orbitals are the lowest in energy and the corresponding a 1g* and t2g* antibonding orbitals
the highest in energy
The eg and eg* orbital orbitals arising from the 3d orbitals are displaced less from their barycenter because of
poorer overlap