Speciation‐Controlled C–F Bond Functionalization Enabled by Zwitterionic Pnictinidenes

Abstract

ABSTRACT Low‐valent pnictogen systems have recently emerged as redox catalysts for C–F activation. However, catalytic turnover has remained largely restricted to hydrodefluorination pathways reliant on metallomimetic reductive elimination. Herein, we report a defluorinative functionalization platform mediated by zwitterionic pnictinidenes that enables the formation of diverse C–X bonds (X = C, O, S, N, P, Se) from polyfluoro(hetero)arenes under mild conditions. Combined experimental and DFT studies reveal that, although a Sb(I)/Sb(III) redox cycle could be accessed, catalysis instead proceeds through Sb(III)–F species that promote C–F substitution via a redox‐neutral manifold. These findings establish catalyst speciation as a decisive mechanistic branch point, showing how strategies to modulate ligand scrambling events may enable alternative pnictogen‐based redox or redox‐neutral manifolds.