Competitive Coordination of Metals by Phosphorus and Sulfur in Complexes with Polydentate Ligands Containing P(III)-S Bonds

A series of complexes of thiophosphites with transition metals has been studied by X-ray single crystal diffraction: CuHalLP(SR)3, CuHalLP(SR)3LNCMe, CuBrLP(SEt)2NEt2, CuSCNLP(SR)3, CpMn(CO)2LP(SR)3, ArCr(CO)2LP(SR)3, with Hal = Cl, Br, I and R = Me, Et, Pr, i-Pr, Bu, Ph. Depending on the metal center, substituents R at sulfur, the conditions of reactions and crystal growth, different coordination modes have been observed: “classical” monodentate binding via phosphorus, unusual bidentate mode with participation of both P and S donor atoms of the ambident P – S system, as well as both monodentate and bidentate modes in one complex.