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Chemistry 3820 Lecture Notes

Dr. M. Gerken

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8. Coordination Compounds and MO Theory


8.1 Molecular orbital diagram of octahedral coordination complexes.
The valence atomic orbitals that are located on the transition-metal centre are the s, p, and d orbitals, which have A1g, T1u,
symmetry,
and
(Eg/T2g)
respectively. Ignoring any ligand
-orbitals, we have to consider
only six linear combinations of
atomic ligand -orbitals. In
principle, we have three choices
of ligand -orbitals: s-orbitals, p
orbitals (those p orbitals that point
directly towards the central atom),
and the sp3 hybrid orbitals that
point towards the metal centre.
The latter mix hybridization,
which is strictly based on VB
theory, with MO theory and,
therefore, we wont use that
description. The s orbitals of the
ligands are usually too low in
energy, since the ligating atom is
usually more electronegative than
the central atom; therefore, the p
orbitals are the -orbitals of
choice. On the right-hand side, the
transition-metal valence orbitals
are depicted together with the
symmetry-adapted ligand orbital
of appropriate symmetry. The
SAOs are usually depicted as s
orbitals, providing us with the
correct relative signs of the orbital
lobes that point towards the
central atom. As discussed above,
you have to substitute the ligand s
orbitals with p orbitals. We can easily see that no linear combination of ligand -orbitals has the correct symmetry (t2g) to
interact with the dxy, dxz, and dyz metal orbitals. The
resulting MO diagram produces six bonding MOs: a1g, t1u,
and eg; three non-bonding MOs: t2g; and six anti-bonding
molecular orbitals: eg*, a1g*, and t1u*. The six bonding
MOs represent the six dative -bonds in an octahedral
complex; they have primarily ligand character. Now we
can but our crude electrostatic ligand-field-splitting picture
into a broader MO theoretical context. The octahedral
ligand field splitting is the splitting between the nonbonding t2g orbitals and the mildly anti-bonding eg*
orbitals; both sets of orbitals have metal character and are
filled with electrons supplied by the transition metal.
Hence, it is clear why any electron residing in the eg*
orbital destabilizes the complex.
When placing electrons into this bonding scheme,
there will be 12 electrons contributed by the ligands. If we
fill the t2g orbital set completely (with six electrons) we
reach 18 electrons, which is a particularly stable electron
configuration. This so-called 18-electron rule states that
18 valence electrons are optimal for a transition-metal
complex. This is the transition-metal analogue to the octet
rule. Note, that there will be many deviations from this
rule, since deficiencies in the t2g set do not alter the

Chemistry 3820 Lecture Notes

Dr. M. Gerken

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bonding, and the 2eg set is only weakly antibonding, and therefore, can be occupied without greatly perturbing the bonding.
Nevertheless, some of the most stable, unreactive metal complexes are indeed formed with metals having a d6 configuration. The
18-electron rule becomes particularly important for complexes with large ligand-field splitting.
8.2 Octahedral coordination complexes with -donor ligands.
So far, we have only considered -donor ligands (-bases). However, the metal t2g
orbitals have the correct symmetry for -bonding with ligand p orbitals, as shown
in the figure on the right-hand side. The SAOs with t2g symmetry are shown

below.
In the presence of p orbitals
(bonding orbitals) on the ligands a splitting of the t2g orbitals results, producing bonding and antibonding t2g sets that have filled
p orbitals The p orbitals on the ligand such as Cl-, Br-, H2O are filled and donate their electrons into the bonding t2g MO. The
formerly non-bonding metal t2g orbitals are elevated, effectively reducing the ligand-field splitting. In general -donor ligands (bases) will cause small ligand-field splitting, though they are quite strongly bonded to the metal centre.

8.3 Octahedral coordination complexes with -acceptor ligands.


In the case where empty * orbitals are accessible on the ligand, interaction between these antibonding ligand orbitals and
the metal t2g orbitals is possible. The splitting gives metal-based t2g molecular orbitals and ligand-based antibonding t2g*
molecular orbitals. Since the energy of the t2g set is lowered the ligand field splitting, O, is increased. Typical examples for acceptor ligands are CO, CN-, and N2, which have low-lying empty * orbitals. For CO, the * has its largest amplitude on the C
atom, which can accept electrons from the metal. In contrast the bonding orbital of CO is low in energy and is largely localized
on the O atom. Hence, the -donor character of carbon-bonded CO is very low.
The ligand-field splitting, O, increases in the sequence:
-donor < weak donor < no effect < acceptor
Representative ligands that match these classes are:
< PR3 < CO
I- < Br- < Cl- < F- < H2O < NH3
-donor < weak donor < no effect < acceptor
Notable examples where the -bonding effect dominates include CH3- and H-.

Chemistry 3820 Lecture Notes

Dr. M. Gerken

8.4 Molecular orbital diagram of tetrahedral coordination


complexes.
Using the character tables of the tetrahedral point group the metal
s, (px,py,pz), (dxy,dxz,dyz), and (dz2, dx2-y2) orbitals can be labeled
with the a1, t2, t2, and e symmetry labels respectively. The a1 and
t2 metal orbitals can interact with the four symmetry-adapted
ligand orbitals (see SAOs for Td). As the result, the e orbital
set is non-bonding and one t2 set is weakly anti-bonding; the
energy difference between these orbitals is the ligand field
splitting, T. As mentioned above, the ligand field splitting in
tetrahedral complexes is 4/9 O. The small size of the ligand field
will never force a low-spin configuration.
Try to construct a MO diagram for a square-planar coordination.
How many valence electrons will results in a particularly stable
electron configuration? Does it differ from 18, which we derived
for octahedral complexes?

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