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

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.
Borylenes of the form (CAAC)(NHC)BY (Y = CN, NCS; CAAC = cyclic alkyl(amino)carbene; NHC = N-heterocyclic carbene) coordinate to group 6 carbonyl complexes via Y, and show reversible boron-centered Brønsted basicity and one-electron oxidation.