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.