Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion

邻位碳硼烷基取代的三配位硼烷自由基阴离子的合成与结构

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Abstract

Bis(1-(4-tolyl)-carboran-2-yl)-(4-tolyl)-borane [(1-(4-MeC(6) H(4) )-closo-1,2-C(2) B(10) H(10) -2-)(2) (4-MeC(6) H(4) )B] (1), a new bis(o-carboranyl)-(R)-borane was synthesised by lithiation of the o-carboranyl precursor and subsequent salt metathesis reaction with (4-tolyl)BBr(2) . Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one-electron first reduction. In a selective reduction experiment the corresponding paramagnetic radical anion 1(.-) was isolated and characterized. Single-crystal structure analyses allow an in-depth comparison of 1, 1(.-) , their calculated geometries, and the S(1) excited state of 1. Photophysical studies of 1 show a charge transfer (CT) emission with low quantum yield in solution but a strong increase in the solid state. TD-DFT calculations were used to identify transition-relevant orbitals.

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