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Durham e-Theses
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Studies of the synthesis and derivative chemistry of icosahedral carboranes

Lane, Richard A. (1982) Studies of the synthesis and derivative chemistry of icosahedral carboranes. Doctoral thesis, Durham University.



As part of the general study of icosahedral carborane chemistry a comprehensive literature survey is presented with references. Investigations of the preparative routes to ortho-carborane, 1-methyl-o-carborane and some carborane polymers showed that improvements on existing literature methods could be made. In the synthesis of possible carborane-polymer precursors, several coupled carborane systems were investigated. These included C-C',B-B' direct cage coupling reactions and coupling via short alkyl chains. Reactions of MeƟLi (Ɵ= -CB(_10)HC-) with boron chlorides produced the previously unreported boron coupled carboranes (MeƟ)(_2)BR, (R=C1,OH, Ph) and MeƟBPh(_2). Three carborane cages could not be bonded to a singleboron atom. The previously unreported di-(3,3'-o-carboranyl)-N,N-r 12-piperazine was prepared from the [HƟH](^2-) anion. Studies were made of the reaction of MeƟLi with ICN and (CN)(_2). An attempted ortho-metallation reaction with SnCl(_4) MeƟLi and PhCN yielded an interesting dicyclic tin adduct, SnCl(_4). [(PhCN)(_3)](_2). The reactions of C(_2)B(_9)H(_11)(^2-) with tin, germanium and silicon tetrachlorides produced a new class of dicarboranyl metal "sandwich" compounds for which a novel tilted cage structure was proposed. Zinc metallocarboranes could not be synthesised. Hot atom chemistry was employed in attempts to prepare main group metallocarboranes by polyhedral expansion.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1982
Copyright:Copyright of this thesis is held by the author
Deposited On:16 Jul 2013 10:59

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