The Dimethylbismuth Cation: Entry Into Dative Bi−Bi Bonding and Unconventional Methyl Exchange

The isolation of simple, fundamentally important, and highly reactive organometallic compounds remains among the most challenging tasks in synthetic chemistry. The detailed characterization of such compounds is key to the discovery of novel bonding scenarios and reactivity. The dimethylbismuth cation, [BiMe(2)(SbF(6))] (1), has been isolated and characterized. Its reaction with BiMe(3) gives access to an unprecedented dative bond, a Bi→Bi donor–acceptor interaction. The exchange of methyl groups (arguably the simplest hydrocarbon moiety) between different metal atoms is among the most principal types of reactions in organometallic chemistry. The reaction of 1 with BiMe(3) enables an S(E)2(back)‐type methyl exchange, which is, for the first time, investigated in detail for isolable, (pseudo‐)homoleptic main‐group compounds.