Isolation of Cyclic(Alkyl)(Amino) Carbene–Bismuthinidene Mediated by a Beryllium(0) Complex

The long‐sought carbene–bismuthinidene, (CAAC)Bi(Ph), has been synthesized. Notably, this represents both the first example of a carbene‐stabilized subvalent bismuth complex and the extension of the carbene‐pnictinidene concept to a non‐toxic metallic element (Bi). The bonding has been investigated by single‐crystal X‐ray diffraction studies and DFT calculations. This report also highlights the hitherto unknown reducing and ligand transfer capability of a beryllium(0) complex. The first carbene‐stabilized subvalent bismuth complex has been synthesized through reduction by a Be0 complex. Notably, this represents both the first example of a carbene‐stabilized subvalent bismuth complex and the extension of the carbene–pnictinidene concept to a non‐toxic metallic element (Bi; see scheme).