Chapter 1 provides an overview of the oxidation of methane by platinum salts known as
Shilov chemistry. This includes platinum complexes used for the selective oxidation of
methane to methyl bisulfate. Attention is paid to model platinum complexes that have been
synthesised to explore the oxidation of methane using dioxygen as the oxidant.
Chapter 2 describes two sets of tridentate N donor ligands that have been synthesised. The
first set contains 6,6ʹʹ-disubstituted-2,2ʹ:6ʹ,2ʹʹ-terpyridine ligands, of these two new ligands
6,6ʹʹ-di(methylamino)-2,2ʹ:6ʹ,2ʹʹ-terpyridine and 6,6ʹʹ-dimethoxy-2,2ʹ:6ʹ,2ʹʹ-terpyridine have
been synthesised and fully characterised. The second set contains non-terpyridine tridentate
ligands. The synthesis and characterisation of novel cationic platinum(II) methyl complexes
bearing these ligands is described in Chapter 3. The structures of some of these complexes
have been determined by X-ray crystallography. Further, the reactivity of the complexes
towards dioxygen is reported and how different reactivity is imparted by the different ligands
is discussed. The ability of some of these platinum(II) methyl complexes to insert dioxygen
into their M-Me bonds arises from the steric interaction between the Pt-Me ligand and the
substituents in the 6- and 6ʹʹ-positions on the terpyridine ligand.
Chapter 4 describes a study into the mechanism of the insertion of dioxygen into a Pt-Me
bond. This includes deuterium labelling experiments, which led to the discovery of the
exchange of methyl ligands between platinum(II) and palladium(II) centres. A mechanism
for this exchange involving the formation of a MII-MII dimer is proposed. In addition, the
decomposition of a palladium(II) methylperoxo complex to give an intriguing new
metallacyclic hemiacetal alkoxide complex is described. A possible mechanism for the
formation of this new palladium(II) complex is discussed.
The synthesis and characterisation of the new compounds discussed in Chapters 2-4 are
reported in Chapter 5.