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

摘要

A series of complexes of thiophosphites with transition metals has been studied by X-ray single crystal diffraction: CuHal centre dot P(SR)_3, CuHal centre dot P(SR)_3 centre dot NCMe, CuBr centre dot P(SEt)_2NEt_2, CuSCN centre dot P(SR)_3, CpMn(CO)_2 centre dot P(SR)_3, ArCr(CO)_2 centre dot P(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.