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

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.

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Article information


Submitted
19 Mar 2021
Accepted
04 May 2021
First published
04 May 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021, Accepted Manuscript
Article type
Edge Article

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

S. Hagspiel, D. Elezi, M. Arrowsmith, F. Fantuzzi, A. Vargas, A. Rempel, M. Härterich, I. Krummenacher and H. Braunschweig, Chem. Sci., 2021, Accepted Manuscript , DOI: 10.1039/D1SC01580J

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