Dithiocarbamate Ligands as Building-Blocks in the Coordination Chemistry of Gold.

The monodentate dithiocarbamate complexes [Au(2)(S(2)CNR(2))(2){&mgr;-(PPh(2))(2)C=CH(2)}] (R = Me (1), Et (2), Bz (3)) are obtained by reaction of [Au(2)Cl(2){&mgr;-(PPh(2))(2)C=CH(2)}] with NaS(2)CNR(2). The free sulfur atoms in complex 2 can subsequently be used to coordinate a third metal center, giving the trinuclear derivatives [Au(2)M(&mgr;-S(2)CNEt(2))(2){&mgr;-(PPh(2))(2)C=CH(2)}]X (X = ClO(4), M = Au (5), Ag (6); X = PF(6), M = Cu (7)). The dinuclear tricoordinate gold(I) complexes [Au(2)(&mgr;-S(2)CNEt(2)){&mgr;-(PPh(2))(2)C=CH(2)}(2)]ClO(4) (8) and [Au(2)(&mgr;-S(2)CNEt(2)){&mgr;-(PPh(2))(2)C=CH(2)}(PPh(3))(2)]ClO(4) (9) are obtained by reaction of [Au(2)(&mgr;-S(2)CNEt(2)){&mgr;-(PPh(2))(2)C=CH(2)}]ClO(4) (4) with (PPh(2))(2)C=CH(2) or PPh(3). The former is also obtained by reaction of [Au(2){&mgr;-(PPh(2))(2)C=CH(2)}(2)](ClO(4))(2) with sodium N,N-diethyldithiocarbamate (1:1). The crystal structures of complexes 2 and 8 are established by X-ray crystallography.