Tris-mercaptophenylphosphine complexes of rhenium: Synthesis, reactivity and structural characterization

Reactions of rhenium(III) precursers with tris-(ortho-mercaptophenyl)phosphine (PS3) followed by neutral donor ligands is reported. The addition of P(SLi)3 to [ReBr3(THT)3] followed by excess isonitrile gives the octahedral [PS3Re(CNiPr)2]. This reaction also generates [PS3Re(CNiPr)]. These complexes are structurally characterized, with the five-coordinate species displaying trigonal bipyramidal geometry and the six-coordinate species displaying distorted octahedral geometry. The decomposition product [(S2PS-SPS2)Re] is also isolated during the separation of the two complexes. This neutral complex displays coordination through two phosphine and four thiolate moieties, with a disulfide bridge that links the remaining sulfurs.