Complexes with S-Donor Ligands. 6.<sup>†</sup> Synthesis of the First Family of (Trithiocarbonato)gold Complexes. Crystal Structure of [(PPh<sub>3</sub>)<sub>2</sub>N][AuCl<sub>2</sub>(CS<sub>3</sub>)]
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[(PPh3)2N][Au(SH)2] reacts with CS2 in acetone to give [(PPh3)2N]2[Au2(CS3)2] (1) which reacts with iodine (1:1) or PhICl2 (1:1) to give 2 or 2‘, which is an equimolar mixture of the gold(III) complex [(PPh3)2N][Au(CS3)2] (3) and [(PPh3)2N][AuX2] (X = I, Cl). These mixtures decompose in dichloromethane or acetone solutions giving an insoluble dark-red solid analyzing as the mixed-valence complex [(PPh3)2N][AuIn{AuIII(CS3)2}n+1] (4) with an average n value of 6. The best method to prepare 3 is by reacting 2 with PTo3 (To = C6H4Me-4). The reaction of 4 with [Et2NC(S)S]2 gives [Au(S2CCNEt2)2][Au(CS3)2] (5), which can also be obtained by reacting 3 with [Au(S2CNEt2)2]ClO4. The complex [(PPh3)2N][AuCl2(CS3)] (6) can be obtained by reacting 3 with PhICl2 (1:1) or 1 with PhICl2 (1:2). By reaction of 6 with an excess of NaBr, the complex [(PPh3)2N][AuBr2(CS3)] (7) can be isolated. Iodine reacts with 3 (1:1) to give [(PPh3)2N][AuI2(CS3)] (8). Cationic complexes [Au(CS3)(LL)]CF3SO3 [LL = 1,10-phenanthroline (phen) (9), 2,2‘-bipyridyl (bipy) (10)] can be obtained by reacting 6 with TlO3SCF3 and the corresponding bidentate ligand (1:2:1). Complex 6 crystallizes in the triclinic system, space group P1̄, with a = 9.482(2) Å, b = 11.888(2) Å, c = 17.303(2) Å, α = 108.236(6)°, β = 93.340(10)°, γ = 95.605(10)°, V = 1835.5 Å3, and Z = 2. The structure was refined to values of R1 = 0.0393 [I > 2σ(I)] and wR2 = 0.0970 (all data). The planar coordination at the gold atom is distorted by the bite of the CS3 ligand [the S(2)−Au−S(1) angle is only 74.49(7)°]. The CSAu bond distances are 1.743(7) and 1.748(7) Å, whereas the CSexo bond is much shorter at 1.608(7) Å.
