A stable rhodium-coordinated carbene with a σ⁰π² electronic configuration

Isolable singlet carbenes have universally adopted a σ²π⁰ electronic state, making them σ-donors and π-acceptors. We present a rhodium-coordinated, cationic cyclic diphosphinocarbene with a σ⁰π² ground state configuration. Nuclear magnetic resonance spectroscopy studies show a carbene carbon chemical shift below -30.0 parts per million. X-ray crystallography reveals a planar RhP₂C configuration. Quantum chemical calculations rationalize how σ-electron delocalization/donation and π-electron negative hyperconjugation together stabilize the formally vacant σ orbital and the filled π orbital at the carbene center. In contrast to traditional carbene counterparts this carbene can undergo synthetic transformations with both a Lewis base and a silver salt, producing a Lewis acid/base adduct and a silver π-complex, respectively. Exhibiting ambiphilic reactivity, it can also form a ketenimine through reaction with an isocyanide.