Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

Abstract We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)‐stabilized bismuth complexes, which feature low‐coordinate cationic bismuth centers with C=Bi multiple‐bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2(9) and [(CDC)BiBr(THF)3][NTf2]2(12), and trication [(CDC)2Bi][NTf2]3(13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2(7) and (CDC)BiBr3(10). Notably, the dications and trication exhibit C Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non‐reductive route to C−Bi π‐bonding character. The CDC‐[Bi] complexes (7–13) were compared with related NHC‐[Bi] complexes (1,3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low‐coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.