Ag(I) and Cu(I) complexes of tetramethyldiphosphinedisulfide: synthesis and structure

Liu, H., Calhorda, M.J., Drew, M.G.B. and Felix, V. (2003) Ag(I) and Cu(I) complexes of tetramethyldiphosphinedisulfide: synthesis and structure. Inorganica Chimica Acta, 347. pp. 175-180. ISSN 0020-1693 doi: 10.1016/S0020-1693(02)01456-1

Abstract/Summary

Reaction of [M(NCCH3)(4)][PF6] (M = Ag, Cu) with the S2P2Me4 ligand in dichloromethane solution led to substitution of all the nitrile ligands by two molecules of the sulfur ligand, affording the new species [Ag(S2P2Me4)(2)][PF6] (1) and [Cu(S2P2Me4)(2)][PF6] (2). The structures of these complexes were determined by single crystal X-ray diffraction. showing the expected tetrahedral coordination around each metal. Density functional theory (DFT) calculations confirmed the different geometries and energies of the free and coordinated ligand, and provided a very good reproduction of the experimental structures, both for Ag and Cu. The lengths of the S=P bonds are barely affected by coordination, indicating that the pi bond is not important in binding to the metal. (C) 2002 Elsevier Science B.V. All rights reserved.