The stabilisation of reduced carboranes
Tricas Laliena, Hugo
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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 expansion chemistry. 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 synthesised. Appendix 2 (provided on compact disc) gives the appropriate crystallographic files in RTF and CIF format.