The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ 3 -P compound in the hexaphenylcarbodiphosphoranyl-based pincer-type ligand (1 + ) are reported. 1 + reacts with electron-poor fluoroarenes via an oxidative additiontype 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.

Geometrically constrained, square pyramidal phosphoranide was synthesized, and its reactivity study showed that it is both a nucleophile and reductant.