Hagspiel, Stephan, Elezi, Dren, Arrowsmith, Merle, Fantuzzi, Felipe, Vargas, Alfredo, Rempel, Anna, Härterich, Marcel, Krummenacher, Ivo, Braunschweig, Holger (2021) Reactivity of cyano- and isothiocyanatoborylenes: metal coordination, one-electron oxidation and boron-centred Brønsted basicity. Chemical Science, 12 . pp. 7937-7942. ISSN 2041-6520. E-ISSN 2041-6539. (doi:10.1039/D1SC01580J) (KAR id:96291)
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| Official URL: https://doi.org/10.1039/D1SC01580J |
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Abstract
Doubly base-stabilised cyano- and isothiocyanatoborylenes of the form LL′BY (L = CAAC = cyclic alkyl(amino)carbene; L′ = NHC = N-heterocyclic carbene; Y = CN, NCS) coordinate to group 6 carbonyl complexes via the terminal donor of the pseudohalide substituent and undergo facile and fully reversible one-electron oxidation to the corresponding boryl radical cations [LL′BY]˙+. Furthermore, calculations show that the borylenes have very similar proton affinities, both to each other and to NHC superbases. However, while the protonation of LL′B(CN) with PhSH yielding [LL′BH(CN)+][PhS−] is fully reversible, that of LL′B(NCS) is rendered irreversible by a subsequent B-to-CCAAC hydrogen shift and nucleophilic attack of PhS− at boron.
| Item Type: | Article |
|---|---|
| DOI/Identification number: | 10.1039/D1SC01580J |
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Divisions > Division of Natural Sciences > Chemistry and Forensics |
| Depositing User: | Felipe Fantuzzi |
| Date Deposited: | 18 Aug 2022 09:06 UTC |
| Last Modified: | 19 Aug 2022 09:10 UTC |
| Resource URI: | https://kar.kent.ac.uk/id/eprint/96291 (The current URI for this page, for reference purposes) |
| Hagspiel, Stephan: |  https://orcid.org/0000-0002-6049-6007 |
| Arrowsmith, Merle: | https://orcid.org/0000-0003-1449-5932 |
| Fantuzzi, Felipe: | https://orcid.org/0000-0002-8200-8262 |
| Vargas, Alfredo: | https://orcid.org/0000-0001-7491-791X |
| Härterich, Marcel: | https://orcid.org/0000-0002-2794-5202 |
| Krummenacher, Ivo: | https://orcid.org/0000-0001-9537-1506 |
| Braunschweig, Holger: | https://orcid.org/0000-0001-9264-1726 |
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