Ambiphilic Reactivity and Switchable Methyl Transfer at a T‑Shaped Bi(NNN) Complex Enabled by a Redox-Active Pincer Ligand

We report the transition-metal-like reactivity of a geometrically constrained, ambiphilic bismuth(III) trisamide. Planarization of the Bi(III) center unlocks Bi–C bond formation when reacted with mild electrophiles (alkyl iodides and triflates) accompanied by two-electron oxidation of the utilized NNN pincer ligand. The preservation of the bismuth oxidation state is confirmed by single-crystal X-ray diffraction and X-ray absorption spectroscopy and corroborated by theoretical calculations. Sequential reduction of the oxidized ligand framework alters the reactivity of a generated Bi–Me unit, enabling controlled access to methyl cation, radical, and anion equivalents. The full [Bi(Me)(NNN)]+/•/– redox series was comprehensively characterized using NMR and EPR spectroscopy as well as spectro-electrochemistry. This work represents the first example of ligand-assisted, redox-neutral C–X bond splitting at bismuth, establishing a new paradigm for synthetic bismuth chemistry.