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 σ 3 -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 P III -center, yielding new fluorophosphorane-type species (P V ). This reactivity of 1 + was used in the catalytic hydrodefluorination of Ar-F bonds with PhSiH 3 , 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.