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Reactivity of cyano- and isothiocyanatoborylenes: metal coordination, one-electron oxidation and boron-centred Brønsted basicity

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

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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