Molecular Orbital Theory

Of Transition Metal Complexes

 ML 6n- 6L -
Cr(+2)
σs* A1g*

T1u*
σp*
4p

eg*

{px, py}
4s
10Dq

3d t2g
p

s
}12e-
{px, py}

eg

σp T1u

σs
A1g
}

}
 P i- Donor Ligands (small 10Dq) P i- Acceptor Ligands (Backbonding –large 10Dq)
M2+ ML6 6L M2+ ML6 6L

Sigma antibonding Sigma antibonding

orbitals orbitals

np np

t2g (π∗)
σ∗3 (eg) σ∗3 (eg)
t 2g (π∗) empty π acceptor orbitals
10Dq
ns ns 10Dq σ donor orbitals
filled π donor orbitals

σ donor orbitals

(n-1)d (n-1)d
t2g (π) t2g (π)

Sigma bonding Sigma bonding

framework framework
12e- 12e-
(from ligands) (from ligands)
CO≈CN->PR3>NH3>H2O>OH->F->Cl->S2->I-

Eg(σ*)

10Dq

π π (nonbonding) π*
Charge Transfer Spectrum
Charge Transfer Bands
Ruthenium Trisbipyridine
[Ru(Bpy)3]2+
 Prussian Blue

Studied for 300 years!

What coordination
complex is better Fe(II)-CN-Fe(III)
understood?