Syntheses and crystal structures of coinage metal thioether-thiolato complexes

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