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-C(CAAC) hydrogen shift and nucleophilic attack of PhS(-) at boron.