Syntheses and Crystal Structures of Coinage Metal Thioether-Thiolato Complexes

Copper(I), silver(I), and two gold(I) complexes of the type (Ph3P)nM(L) [n = 1, 2, 3; L = 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate (La), 1,2-dicyano-1-(methylthio)ethene-2-thiolate (Lb)] have been synthesized. The molecular structure of these complexes was determined by X-ray crystallography and shows differences in the coordinated sulfur atoms as well as in the coordination geometry of these (Ph3P)nM(L) complexes. In (Ph3P)2Cu(L) (2), the thioether thiolate ligands act as bidentate ligands, whereas in the silver and gold complexes (Ph3P)3Ag(L) (3) and (Ph3P)2Au(L) (4), only the thiolate sulfur is coordinated. Dissociation of one of the phosphane ligands of (Ph3P)2Au(La) (4a) occurs in boiling acetone and a linear two-coordinate gold(I) center is obtained, (Ph3P)Au(La) (5a).