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.