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

The monodentate dithiocarbamate complexes [Au2(S2CNR2)2{μ-(PPh2)2CCH2}] (R = Me (1), Et (2), Bz (3))
are obtained by reaction of [Au2Cl2{μ-(PPh2)2C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(μ-S2CNEt2)2{μ-(PPh2)2CCH2}]X (X = ClO4, M = Au (5), Ag (6); X = PF6, M = Cu (7)). The dinuclear tricoordinate
gold(I) complexes [Au2(μ-S2CNEt2){μ-(PPh2)2CCH2}2]ClO4 (8) and [Au2(μ-S2CNEt2){μ-(PPh2)2CCH2}(PPh3)2]ClO4 (9) are obtained by reaction of [Au2(μ-S2CNEt2){μ-(PPh2)2CCH2}]ClO4 (4) with (PPh2)2CCH2 or PPh3.
The former is also obtained by reaction of [Au2{μ-(PPh2)2C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.