Chemical and electrochemical substitution of monocarbon carboranes; rationalisation of experimental behaviour of derivatives of [nido-7-CB10H13]? and [closo-1-CB11H12]?

Abstract
Controlled substitution of the monocarboranes [nido-7-CB10H13], nido-7-Me3N-7-CB10H12, and closo-1 -Me3N-1-CB11H11has been achieved by chemical and electrochemical means. The position of boron substitution in 7-Me3N-7-CB10H12derivatives depends on the experimental method. Chloride substitution at B(4) was achieved by electrophilic (electrochemical) methods, whereas HCl–AlCl3resulted in substitution at B(9). Substitution at B(8) was obtained through a nido-closo-nido sequence of oxidation and ligand addition. The compounds were structurally characterised by 11B–11B correlation n.m.r. spectroscopy. The experimental data were correlated with AM1 calculations.

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