New chemistry of 1,1'-bis(o-carborane)

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. In the later part the focus changes to 1,1′-bis(o-carborane). Chapter 2 describes the attempted two electron reduction/metallation and single cage decapitation/metallation chemistry of 1,1′-bis(o-carborane). Also described are the analysis of two dimensional 11B-11B correlation spectra of all the products and the cal-culation of weighted average 11B chemical shifts of the individual cage components of these products which are discussed with respect to the parent compound. Chapter 3 describes the double cage decapitation of 1,1′-bis(o-carborane) with excess KOH and metallation with {(arene)Ru} and {CpCo} fragments at room temperature. Metallation with {(arene)Ru} resulted in two products whereas metallation with {CpCo} yielded the same two structure types plus a third product. Also discussed are the room temperature isomerisations observed. Chapter 4 reports the double cage decapitation of 1,1′-bis(o-carborane) and metallation with {(dmpe)Ni} fragments, and discusses diastereoisomers obtained for the first time. Also discussed are the methylation of 1,1′-bis(o-carborane) and the results obtained from decapitation followed by deprotonation and metallation of this. Chapter 5 gives full details of the experimental procedures undertaken and also pro-vides spectroscopic and analytical data for all new compounds reported herein. Appendix 1 provides details of the crystal structure determinations of the compounds synthesised. Appendix 2 (provided on compact disk) gives the appropriate crystallographic files in RTF and CIF format.