TY  - JOUR
A1  - Krebs, Johannes
A1  - Haehnel, Martin
A1  - Krummenacher, Ivo
A1  - Friedrich, Alexandra
A1  - Braunschweig, Holger
A1  - Finze, Maik
A1  - Ji, Lei
A1  - Marder, Todd B.
T1  - Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion
JF  - Chemistry—A European Journal
N2  - 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.
KW  - Wade’s rules
KW  - carborane
KW  - charge transfer
KW  - radical
KW  - threecoordinate boron
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256841
VL  - 27
IS  - 31
ER  -