Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar-F Bonds

The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ3-P compound in the hexaphenyl-carbodiphosphoranyl-based pincer-type ligand (1+) are reported. 1+ reacts with electron-poor fluoroarenes via an oxidative addition-type reaction of the C-F bond to the PIII-center, yielding new fluorophosphorane-type species (PV). This reactivity of 1+ was used in the catalytic hydrodefluorination of Ar-F bonds with PhSiH3, and in a catalytic C-N bond-forming cross-coupling reactions between fluoroarenes and aminosilanes. Importantly, 1+ in these catalytic reactions closely mimics the mode of action of the transition metal-based catalysts.