Zwitterionic Pnictinidenes in Catalytic Defluorinative Functionalization: Beyond Redox Hydrodefluorination

Functionalization of fluorocarbons represents a central challenge in synthetic chemistry due to the exceptional strength of C–F bonds and the persistence of such compounds in the environment. Herein, we report the catalytic defluorinative functionalization of polyfluoro(hetero)arenes mediated by zwitterionic Sb and Bi species. These bis(NHC)borate-stabilized complexes enable C–X bond formation (X = C, O, S, N, P, Se) under mild conditions and a broad substrate scope. Mechanistic investigations, supported by DFT, reveal a dual landscape of redox and redox-neutral pathways, underscoring the metallomimetic behaviour of pnictinidenes in oxidative addition and highlighting the catalytic potential of pnictogen fluoride species. This work establishes zwitterionic Sb and Bi complexes as versatile catalysts for C–F bond activation, providing a general platform for main-group catalysis in defluorofunctionalization chemistry.