Molecular orbital theory approach to

bonding in transition metal complexes

 Molecular orbital (MO) theory considers the overlap of
atomic orbitals, of matching symmetry and comparable
energy, to form molecular orbitals.

 When atomic orbital wave functions are combined, they

generate equal numbers of bonding and antibonding
molecular orbitals.

 The bonding MO is always lower in energy than the

corresponding antibonding MO.

 Electrons occupy the molecular orbitals in order of their

increasing energy in accordance with the aufbau principal.

Bond-Order = Electrons in bonding MOs – Electrons in antibonding MOs

2
Molecular orbital approach to bonding in octahedral complexes, ML6

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Combinations of atomic orbitals Molecular Orbital

4s a1g

4px
4py t1u
4pz

3dx2 - y2 eg
3dz2

3dxy
3dxz Non-bonding in σ complex t2g
3dyz
_______________________________________________________________________________________________
MO diagram for s-bonded octahedral metal complex
 M.O. Diagram for Tetrahedral Metal Complex

Since the metal 4p and t2 orbitals are of the same symmetry, e → t2 transitions in
Td complexes are less “d-d” than are t2g → eg transitions in Oh complexes. They are
therefore more allowed and have larger absorbtivity values (e)
 Metal-ligand P-bonding interactions

 t2g orbitals (dxy, dxz, dyz) are non-bonding in a s-bonded octahedral

complex

 ligands of P-symmetry overlap with the metal t2g orbitals to form

metal-ligand P-bonds.

 P-unsaturated ligands such as CO, CN- or 1,10-phenanthroline or sulfur

and phosphorus donor ligands (SR2, PR3) with empty t2g-orbitals have
the correct symmetry to overlap with the metal t2g orbitals.
 P-acceptor interactions have the effect of lowering the energy of
the non-bonding t2g orbitals and increasing the magnitude Doct.

This explains why P-acceptor ligands like CO and CN- are strong field ligands, and
why metal carbonyl and metal cyanide complexes are generally low-spin.
P-interactions involving P-donation of electron density from filled p-
orbitals of halides (F- and Cl-) and oxygen donors, to the t2g of the
metal, can have the opposite effect of lowering the magnitude of
Doct. In this case, the t2g electrons of the s-complex, derived from the
metal d orbitals, are pushed into the higher t2g* orbitals and become
antibonding. This has the effect of lowering Doct.

Ligand p (full)
M L e.g. halide ion, X-
RO-

Metal- d (t2g) Ligand - p

Effect of ligand to metal P-donor interactions
P-alkene organometallic complexes

Zeise’s Salt, K[PtCl3(C2H4)]

 P-acceptor interactions have the effect of lowering the energy of
the non-bonding t2g orbitals and increasing the magnitude Doct.

This lowering of the energy of the t2g orbitals also results in strongly bonding
M.O.’s well separated in energy from the antibonding orbitals
 Consequences of P-bonding interactions between
metal and ligand
 Enhanced D-splitting for P-acceptor ligands makes P-unsaturated ligands
like CO, CN- and alkenes very strong-field ligands.

 Stabilization of metals in low oxidation states.

Delocalization of electron density from low oxidation state (electron-rich)
metals into empty ligand orbitals by “back-bonding” enables metals to exist
in formally zero and negative oxidation states (Fe(CO)5, Ni(CO)42-).

 Accounts for organometallic chemistry of P-Acid ligands

 The application of the “18-electron rule” to predict and rationalize

structures of many P-acid organometallic compounds.
Electron donation by P-unsaturated ligands
Examples of 18-electron organometallic complexes with P-
unsaturated (P-acid) ligands
 Metal-ligand interactions involving bonding and
antibonding molecular orbitals of O2

*of O2 (empty)
of O2 (filled)
*

O
O
O
O

Fe Fe

dz2 of Fe (empty) t2g (dxz ,dyz ) of Fe (filled)