Dithiocarbamate ligands as building-blocks in the coordination chemistry of gold

The monodentate dithiocarbamate complexes [AU(2)(S2CNR2)(2){mu-(PPh2)(2)C = CH2}] (R = Me (1), Et (2), Bz (3)) are obtained by reaction of [Au2Cl2{mu-(PPh2)(2)C = CH2}] with NaS2CNR2. The free sulfur atoms in complex 2 can subsequently be used to coordinate a third metal center, giving the trinuclear derivatives [Au2M(mu-S2CNEt2)(2){mu-(PPh2)(2)C = CH2}]X (X = ClO4, M =Au (5), Ag (6); X = PF6, M = Cu (7)f. The dinuclear tricoordinate gold(I) complexes [Au-2(mu-S2CNEt2){mu-(PPh2)(2)C = CH2}(2)]ClO4 (8) and [Au-2(mu-S2CNEt2){mu-(PPh2)(2)C = CH2}.(PPh3)(2)]ClO4 (9) are obtained by reaction of [Au-2(mu-S2CNEt2){mu-(PPh2)(2)C = CH2}]ClO4 (4) with (PPh2)(2)C = CH2 or PPh3. The former is also obtained by reaction of [Au-2{mu-PPh2)(2)C = CH2}(2)](ClO4)(2) with sodium N,N-diethyldithiocarbamate (1:1). The crystal structures of complexes 2 and 8 are established by X-ray crystallography.