Molecular orbital theory of

octahedral complexes

MOHAMMED SHINAN K A
M230427CY
Simple molecular orbital theory can be applied to the sigma bonding of regular octahedral complex
ML6 which belongs to octahedral point group , By four steps we can illustrate how MOT can be
applied to these metal complexes qualitatively through the formalism developed in group theory

1. Classification of metal valence orbitals into sigma symmetry:-in this step we have to determine
which atomic orbitals on the metal ion may be combined to produce a set of six equivalent
hybrid orbitals which in turn may overlap with the orbitals on the ligand situated at six corners
of an octahedron. the coordinate system with appropriate disignations of sigma-hybrid orbitals
can be shown as
The character of RR based on six bond vectors can be shown as

Ꞅ- reduced to – A1g+Eg+T1u
Following six orbitals are required for sigma bonding hybridization with a 1g, eg and t1u symmetry
• a1g : s
• T1u : px, py, pz
• Eg : dz2, d(x2-y2)
2)formation of ligand group orbitals
• The combination of ligand orbitals which have the same symmetry as the metal sigma hybrid orbitals can be worked out by

SALC of AOs by projection operation method. Such combinations on normalisation give LGOs can be constructed alternately

as illustrated below by assuming the ligand sigma orbital is always oriented to the central metal ion with its +ve lobe
• The metal ion s-orbital shown to interact with all the ligand sigma hybrid orbitals leading to LGOs of a 1g symmetry
• The wave function ψa1g corresponding to this proper linear combination can be given by

Ψa1g=1/√6(ø1+ø2+ø3+ø4+ø5 +ø6)
• The metal ion px orbital shown to interact with only L1 and L3 ligand sigma hybrid orbitals leading to

one of the t1u LGOs

The wave function Ψt1ua=1/ √2(ø1-ø3)

• Similarly py and pz on metal ion interact with L2,L4 and L5,L6 respectively .corresponding wave
function are given by

Ψt1ub=1/ √2(ø2-ø4)
Ψt1uc=1/ √2(ø5-ø6)
• The metal ion dx2-y2 interacting with the ligands L1,L4 hybrids leading to one of the e g-LGOs

Ψega=1/ 2(ø1-ø2+ø3-ø4)
• The metal ion dz2 interacting with all the ligand hybrid orbitals leading to one of the eg-LGOs

Ψe b=1/√12(-ø -ø -ø -ø +2ø +2ø )

 3)Formation of molecular orbitals

• The metal ion valence hybrid orbitals and the LGOs of sigma symmetry have the right symmetry
to further combine to give the corresponding MOs, one of bonding and the other of antibonding
in nature. mathematically this can be expressed as
• For a1g
ΨA1g=N1[a1g(s)1/√6(ø1+ø2+ø3+ø4+ø5 +ø6)]
• For t1u
ΨT1U(px)=N2[t1u(px) 1/ √2(ø1-ø3)]
ΨT1U(py)=N3[t1u(py) 1/ √2(ø2-ø4)]
ΨT1U(pz)=N4[t1u(pz) 1/ √2(ø5-ø6)]
• For eg
Ψeg(dx2-y2)=N5[eg(dx2-y2) 1/ 2(ø1-ø2+ø3-ø4)]
Ψeg(dz2)=N6[eg(dz2) 1/√12(-ø1-ø2-ø3-ø4+2ø5 +2ø6)
4)Construction of molecular orbital energy level diagram

• We can only build a qualitative energy level diagram showing the logical ordering of
Mos wih the assumption that
• LGOsns np

In this case the T2g set(dxy,dxz,dyz)of metal orbitals are shown as non-bonding.
The lower energy six bonding MOs assumes primarily the character of ligand and the
higher energy antibonding MOs have the character of metal ion. the BMOs can be
filled with 12 donor electrons from the ligands. The remaining electrons from the
metal ion filled starting from T 2g MO shows A1g,Eg,T1u have largely ligand character and
other have largely metal character