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

[Image: see text] 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.