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

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 AgI, HgII, ZnII, PtII, and PdIIare reported. Crystals of [Cu(bdtm)Cl]·Me2CO are orthorhombic, space group Pna21with a= 17.185(2), b= 13.640(3), c= 12.058(1)A, 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.