A synthetic cycle for aryl C−F substitution comprising oxidative addition, ligand metathesis, and reductive elimination at a C s -symmetric phosphorus triamide (1, P{N[o-NMe-C 6 H 4 ] 2 }) is reported. Reaction of 1 with perfluoroarenes (Ar F − F) results in C−F oxidative addition, yielding fluorophosphoranes 1•[F][Ar F ]. The P-fluoro substituent is exchanged for hydride by treatment with DIBAL-H, generating hydridophosphoranes 1•[H][Ar F ]. Heating of 1•[H][Ar F ] regenerates 1 by C−H reductive elimination of Ar F −H, where experimental and computational studies establish a concerted but highly asynchronous mechanism. The results provide well-characterized examples of the full triad of elementary mechanistic aryl C−X substitution steps at a single main-group site.
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