Sulphur-ligand–metal complexes. Part IV. Copper complexes with bidentate tertiary-phosphine sulphide and selenide ligands and the crystal structure of a three-co-ordinate copper(I) complex

Abstract

The preparation of the following compounds is described: [CuL₂][ClO₄][L = bis(diphenylphosphinothioyl)methane (bdtm), bis(diphenylphosphinothioyl)ethane (bdte),or bis(diphenyIphosphinoselenoyl)methane (bdsm)], [CuLX]_a[L = bdtm, bdte, bdtm, or tetramethyldiphosphine disulphide (tmdpds); n= 1 or 2], and [Cu(bdtm)Cl₂](where spectroscopic evidence suggests a distorted tetrahedral arrangement of ligands). Similar species [CuL₂Cl₂](L = Me₂PhPS or MePh₂PS, L₂= bdte or tmdpds) are detected in solution and have the same tetrahedral stereochemistry. Related complexes of Ag^I, Hg^II, Zn^II, Pt^II, and Pd^IIare reported. Crystals of [Cu(bdtm)Cl]·Me₂CO are orthorhombic, space group Pna2₁with a= 17.185(2), b= 13.640(3), c= 12.058(1)Å, Z= 4. The structure was determined by the heavy-atom method and refined by least-squares methods to R 0.052 for 2 876 reflections measured by diffractometer. The molecule is a three-co-ordinate monomer with the occluded acetone filling a void.