Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar–F Bonds
Karina Chulsky, Irina Malahov, Deependra Bawari, Roman Dobrovetsky
Abstract
High Resolution Image Download MS PowerPoint Slide 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.