Synthetic and structural studies of (hetero)carboranes with contrasting exopolyhedral substituents
Powley, Samuel L.
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Chapter one of this thesis provides a broad introduction to (hetero)borane chemistry, with some more focussed discussion on topics pertaining to the work which comprises this document. It also includes the scope of thesis for this work. Chapter two describes the preparation and characterisation of a substantial number of nitrosocarboranes along with hydroxylamine and Diels-Alder cycloadduct derivatives based on these nitroso-species. This chapter contains improved characterisation of some previously reported compounds, along with novel compounds. Some of these species are characterised crystallographically, including two examples involving crystal growth for diffraction studies by cooling a liquid sample. Chapter three describes the Enhanced Structural Carborane Effect and provides evidence for this phenomenon via comparison of molecular geometry of a series of closely related compounds determined by X-Ray diffraction studies. It also includes investigation into ligand substitution of a ruthenacarborane carbonyl compound, and discussion of the ligand orientation and bond distances of the family of compounds prepared and studied. Chapter four contains experimental details for all of the novel compounds involved in chapters two and three, along with some alternative or improved syntheses for some known compounds.