We will construct a molecular orbital diagram for an octahedral transition

metal complex, which involves (sigma) σ-bonding only. Consider

[Co(NH3)6]3+ as an example.

The metal will use one s, three p, and five d-orbitals for bonding. From the
octahedral character table (it is related to group theory, which is beyond
the scope of this course)

s orbital will give a1g symmetry orbital.

p orbitals will give t1u symmetry orbitals.
dz2, dx2-y2 will give eg symmetry orbitals.
dxz, dyz, dxy will give t2g symmetry orbitals.

Similarly, six ammonia ligands will give six orbitals (a1g + eg + t1u) of a1g, eg
and t1u symmetry, which will form six (sigma) σ-bonds between the cobalt
center and the ammonia ligands.

The molecular orbital diagram for [Co(NH3)6]3+ is pictured below in

following Figure:

Note that:
• There are 18 electrons in the valence shell of [Co(NH3)6]3+, 6 from
Co3+ and 12 from the 6 ammonia molecules.

• Of these 18 electrons, 6 are in the d orbitals. These 6 are in the non-

bonding t2g orbitals.

• The d orbitals split in molecular orbital. The eg orbitals are ANTI-

BONDING.

• The ordering of the molecular orbitals is qualitative guesswork. The

a1g is placed at lowest energy because this orbital involves mainly s-
orbitals, which are lower in energy than p and d-orbitals. The t1u level
comes next and the eg level is highest because the d-orbitls are higher
in energy than either the s or p-orbitals.

1
 a*1g

t*1u
Antibonding MOs.
e*g

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
eg t2g
Co3+ t2g(non-bonding)
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

eg a1g t1u
↑↓ ↑↓ 6NH3
eg

↑↓ ↑↓ ↑↓ Bonding MOs.
t1u

↑↓
a1g
Metal orbitals
(AO of M) MO Ligand group orbitals

Figure 1: Molecular orbital diagram for [CoIII(NH3)6]3+

Co3+ = 1s2, 2s22p6, 3s23p63d6

6
3d 4s 4p 4d

↑↓ ↑ ↑ ↑ ↑ xx xx xx xx xx xx

dxy dxz dyz dx2-y2 dz2, s px py pz

xx = lone pair of electrons contributed by NH3 molecule.

2
A similar MO diagram can be drawn for the complex [CoF6 ]3-.
The energies of the 2p-orbitals on F- are much lower than the
energy of the corresponding orbital on N in NH3.

a*1g

t*1u
Antibonding MOs.

↑ ↑ e*g

↑ ↑ ↑↓ ↑ ↑ ↑↓ ↑ ↑
eg t2g
Co3+ t2g(non-bonding)
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

eg a1g t1u
↑↓ ↑↓ 6F-
eg

↑↓ ↑↓ ↑↓ Bonding MOs.
t1u

↑↓
a1g
Metal orbitals MO Ligand group orbitals
(AO of M)

Figure 2. Molecular orbital diagram for [CoF6]3-.

These above Molecular orbital diagrams are just to remind you

about your CH204 course.

3
Similarly, we can construct the MO energy level diagram of Cr(CO)6

Molecular orbital diagram for [Cr(CO)6]

a*1g

t*1u
Antibonding MOs.
t1u e*g

↓
a1g

↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓
eg t2g
Cr t2g(non-bonding)
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

eg a1g t1u
↑↓ ↑↓ 6 CO
eg

↑↓ ↑↓ ↑↓ Bonding MOs.
t1u

↑↓
a1g
Metal orbitals
(AO of Cr) MO Ligand group (CO) orbitals

Remember that 6 bonding MOs in Cr(CO)6 are filled with the electrons
donated from the HOMO by the six CO molecule.
CO is a monohepto ligand.
CO is also a (pi) π-acid ligand because it can accept the electrons in its
LUMO from the non-bonding (t2g) orbitals of Cr(CO)6.

4
Similarly, we can construct the MO energy level diagram of
[Cr(NH3)5(C2H4)] where C2H4 is a (pi) π-acid ligand.
In this case 6 bonding MOs in [Cr(NH3)5(C2H4)] will be filled
with the five pairs of electrons donated by five NH3 molecules and
a pair of electron from the HOMO of C2H4 molecule.
C2H4 molecule can also accept back donation in its LUMO from
the complex [Cr(NH3)5(C2H4)]. Hence C2H4 molecule is π-acid
ligand.

Try to draw MO energy level diagram of [Cr(NH3)5(C2H4)] where

you also show a MO energy level diagram of C2H4. (This will be
answer of Question 7 (b) (ii) in 2008 final Exam paper).