The work within this thesis describes developments in platinum catalysed
hydrometallation for the synthesis of a range of diverse metalloid scaffolds.

Chapter 1 contains a discussion of the application of organometalloid scaffolds
in modern organic chemistry, as well as the widespread application of platinum
complexes in the synthesis of said scaffolds. Notable developments in the field
are summarised and the generally accepted mechanisms through which these
reactions proceed are discussed.

Chapter 2 examines the limitations of previous platinum complexes in catalysing
selective hydrosilylations and the reasons for these limitations, as well as
discussing the approaches to, and applications of, allylic amines in organic
chemistry. The development of a PtCl2Xantphos catalyst to selectively carry out
the hydrosilylation of propargylic amines and their derivatives is detailed as well
as an investigation of the substrate scope. The synthetic utility of the products is
investigated resulting in the development of a remarkably mild aziridination
procedure.

Chapter 3 builds on the previous aziridination procedure, demonstrating the
applicability of the same sequence to access a range of diverse oxetanes by a
hydrosilylation/cyclisation sequence. Previous approaches to oxetanes are
discussed, as well as the utility of the scaffold in modern organic and medicinal
chemistry. Attempts to expand the methodology to the synthesis of other
heterocycles is also discussed.

Chapter 4 details the study of platinum complexes in the context of
hydrostannylation chemistry. Previous approaches to the scaffold are discussed,
as well as the surprising lack of platinum-based catalyst systems. The effect of
ligand denticity on stereoselectivity is reported, with a ligand controlled
stereodivergency reported. Using a PtCl2(XPhos)2 catalyst system, a range of
diverse organotin scaffolds are synthesized, and the benefits and limitations of
the system in comparison to previous catalysts is discussed. A telescoped hydrometallation/cross-coupling sequence is developed to minimize the need to
handle relatively unstable and toxic stannylated intermediates.

Chapter 5 explores the application of platinum complexes bearing both NHC and
phosphine ligands as hydrosilylation catalysts. The synthesis of a broad range of
imidazolium salts is presented, alongside the synthesis of several platinum
complexes via an organosilver intermediate. The efficacy of the complexes
towards hydrosilylation is evaluated, and their poor performance rationalized in
the context of similar complexes employed in the literature.

Chapter 6 provides overall conclusions from the work presented as well as a
discussion of further avenues of study.

Chapter 7 provides bibliographic data for the thesis. Relevant characterisation
data for novel compounds or compounds prepared by novel routes can be
found at the end of the relevant chapter.