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

Abstract

A series of complexes of thiophosphites with transition metals has been studied by X-ray single crystal diffraction: CuHal«P(SR) 3 , CuHal'P(SR) 3 «NCMe, CuBr-P(SEt) 2 NEt 2 , CuSCN'P(SR) 3 , CpMn(CO) 2 «P(SR) 3 , ArCr(CO) 2 -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.