Synthesis and Structure of an o-Carboranyl-Substituted Three-Coordinate Borane Radical Anion
Please always quote using this URN: urn:nbn:de:bvb:20-opus-256841
- 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 andBis(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.…
Author: | Johannes Krebs, Martin Haehnel, Ivo Krummenacher, Alexandra Friedrich, Holger Braunschweig, Maik Finze, Lei Ji, Todd B. MarderORCiD |
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URN: | urn:nbn:de:bvb:20-opus-256841 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | Chemistry—A European Journal |
Year of Completion: | 2021 |
Volume: | 27 |
Issue: | 31 |
Pagenumber: | 8159–8167 |
Source: | Chemistry—A European Journal 2021, 27(31):8159–8167. DOI: 10.1002/chem.202100938 |
DOI: | https://doi.org/10.1002/chem.202100938 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Tag: | Wade’s rules; carborane; charge transfer; radical; threecoordinate boron |
Release Date: | 2022/03/08 |
Licence (German): | ![]() |