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 stu died by IC-ray single crystal diffraction: CuHal . P(SR)(3), CuHal . P(SR)( 3)NCMe. CuBr . P(SEt)(2)NEt2, CuSCN . P(SR)(3), CpMn(CO)(2). P(SR)(3), ArCr (CO)(2). P(SR)(3), with Hal = Cl, Br, land R = Me, Et, Pr, i-Pr, Bu, Ph. De pending on the metal center, substituents R at sulfur, the conditions of re actions and crystal growth, different coordination modes have been observed : "classical" monodentate binding via phosphorus, unusual bidentate mode wi th 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.