Functionalization of Tetraphosphido Ligands by Heterocumulenes.

Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P ligands. Specifically, the reaction of carbon disulfide (CS) with [K(18c-6)][(Ar*BIAN)Co(η-P)] ([K(18c-6)], 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η:η-PCS)] ([K(18c-6)]), in which CS is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine).