Functionalization of Tetraphosphido Ligands by Heterocumulenes

Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), 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 P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P–P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P–C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).