I3 Coordination Chemistry

Dr M Murrie

Course outline:
revision and extension of some basic concepts (1st row)

magnetic properties & spin crossover

comparison of 2nd and 3rd rows with 1st row lanthanides

electronic spectra

Periodic Table of the Elements

Coordination chemistry is primarily concerned with metal complexes 1st row 2nd row 3rd row

lanthanides

Oxidation states

The group ox. state is never achieved in the 3d series after Mn 3+ ions

The group ox. state is never achieved after group 8 (due to the increase in ionisation energy with increasing nuclear charge)

Metal Geometries Commonly octahedral (Oh), tetrahedral (Td), square planar (D4h) for the first row ions Second and third row d-block elements and the lanthanides often have higher coordination numbers

The spectrochemical series For octahedral complexes, oct increases along the spectrochemical series of ligands Crystal field theory can not explain the order of this series, because it is a purely electrostatic (ionic) model: Why is Cl- a weak field ligand? (oct small) Why is CO a strong field ligand? (oct large) Adapting crystal field theory to include a covalent contribution to the bonding gives ligand field theory

Only orbitals of the same symmetry type have non-zero overlap integral

So, if there are 2 sets of orbitals with the same symmetry (one on the ligands and one on the metal) they will interact However, they will not interact with orbitals of different symmetry

The symmetry adapted combinations of the ligand orbitals in an octahedral complex:

Metal

Complex a1g*

Ligands Overlap of two atomic orbitals, produces two molecular orbitals: one bonding & one antibonding

a1g

a1g a1g

The symmetry adapted combinations of the ligand orbitals in an octahedral complex:

Metal atom

ligands

The symmetry adapted combinations of the ligand orbitals in an octahedral complex:

Key point: there is no combination of ligand orbitals that has the symmetry of the metal t2g orbitals Hence, the metal t2g orbitals do not participate in bonding

Metal atom

Molecular Orbital energy levels of an octahedral complex

Molecular Orbital energy levels of an octahedral complex

Molecular Orbital energy levels of an octahedral complex

Molecular Orbital energy levels of an octahedral complex

MO diagram

The six bonding molecular orbitals are mainly ligand-orbital in character e.g. can accommodate the 12 electrons provided by the six ligand lone pairs

MO diagram Now, n x d electrons are supplied by the metal ion they enter the t2g and eg orbitals qualitatively the same result as crystal field theory! However, note that the t2g orbitals are nonbonding and the eg orbitals are weakly anti-bonding

MO diagram

We can begin to understand why some ligands are strong or weak e.g. a good donor ligand, like NH3, will result in a strong metalligand overlap: hence, a more strongly anti-bonding eg set and a larger oct value

Molecular Orbital energy levels of an octahedral complex

However, to explain the spectrochemical series we must consider what crystal-field theory ignores completely: the formation of bonds with metal d orbitals of the correct symmetry For an octahedral complex, the combinations that can be formed from the ligand orbitals include combinations of t2g symmetry These combinations have net overlap with the metal t2g orbitals, which are no longer non-bonding Key point: this will adjust the energies of the t2g orbitals and hence affect oct

 donor ligands decrease oct

A donor ligand has filled orbitals of symmetry Weak field ligands are able to donate electron density to the metal: e.g. Cl-, Br-, OH-, H2O.

partial MO diagram

A donor ligand has filled orbitals of symmetry Weak field ligands are able to donate electron density to the metal: e.g. Cl-, Br-, OH-, H2O. The previously non-bonding t2g orbitals become weakly anti-bonding Hence, they are raised in energy and closer to the anti-bonding eg orbitals i.e. oct decreases Electrons supplied by the ligand orbitals

 acceptor ligands increase oct

A acceptor ligand has empty orbitals of symmetry Strong field ligands are able to accept electron density from the metal: e.g. CN-, CO (vacant * orbital)

partial MO diagram

A acceptor ligand has empty orbitals of symmetry Strong field ligands are able to accept electron density from the metal: e.g. CN-, CO (vacant * orbital)

The acceptor orbitals on most ligands are higher in energy than metal d orbitals The new bonding combination is lower in energy than the d orbitals themselves i.e. oct increases

Increasing oct donor I-, Br-, Cl-, FOH< weak donor < no effects < acceptor H2O NH3 NR3 CH3HNone have orbitals of symmetry of an appropriate energy PR3, CO CN-