|dc.description.abstract||Chapter 1 presents the most relevant literature in the fields of borane, carborane and
metallacarborane chemistry, providing the reader with an overview of these topics. The
area of supraicosahedral (hetero)carborane chemistry is covered in detail, focusing on
the instability of reduced carborane dianions towards re-oxidation.
Chapter 2 reports the attempted stabilisation of reduced carborane dianions by control
of the cage carbon atom movement. The design and preparation of a rigid tether and its
attachment to meta-carborane are presented, accompanied by a detailed study of the
reduction chemistry of the unprecedented tethered carborane formed.
Chapter 3 introduces the concept of reduced carborane stabilisation by inductive
effects. A series of novel carboranes bearing electron withdrawing fluorinated aryl
groups is reported. The influence of these substituents is investigated in detail by
computational, structural, spectroscopic and electrochemical studies in order to select
the best carborane precursor for polyhedral expansion chemistry.
Chapter 4 describes the polyhedral expansion of selected carboranes. The synthesis
and characterisation of a series of novel supraicosahedral species are presented, together
with an exhaustive discussion of the effect of fluorinated aryl groups in polyhedral
Chapter 5 gives full details of the experimental procedures undertaken and also
provides spectroscopic and analytical data for all the new compounds reported herein.
Appendix 1 provides details of the crystal structure determinations of compounds
Appendix 2 (provided on compact disc) gives the appropriate crystallographic files in
RTF and CIF format.||en_US