Nine- and ten-membered diauracycles with the C3S52- ligand. Crystal structure of NBu4[Au2(μ-C3S5) (μ-CH2PPh2CH2)]

Article abstract of DOI:10.1016/0020-1693(96)05088-8

The synthesis of hetero-bridged dinuclear gold(I) complexes with the C₃S₅^2- (1,3-dithiole-2-thione-4,5-dithiolate) ligand has been tested by different methods: (i) reaction of [Au(μ-L-L)X₂]^n- with Na₂C₃S₅ ethanolic solutions; (ii) reaction of [Au₂(C₃S₅) (AsPh₃)]_n with different bidentate ligands. The resulting complexes Q[Au₂(μ-C₃S₅) (μ-CH₂PPh₂CH₂)] (1), [Au₂(μ-C₃S₅) (μ-dppe)] (2) and Q[Au₂(C₃S₅) (S₂CNR₂)] (R = Me (3), Et (4) or CH₂Ph (5)) have been characterized by analysis, conductivity, IR, ³¹P and ¹H NMR. Complex (PPN)₂[Au(C₃S₅)₂] (6) (PPN = N(PPh₃)₂) has been achieved by reaction of [AuCl(tht)] (tht = tetrahydrothiophene) or [AuCl(AsPh₃)] with Na₂C₃S₅ and addition of (PPN)Cl. Reaction of 1 with (TTF)₃(BF₄)₂ (TTF = tetrathiafulvalene) affords (TTF) [Au₂(C₃S₅) (CH₂PPh₂CH₂)] (7) and reaction of 6 with AgClO₄ gives a polynuclear complex [Au₂Ag₂(C₃S₅)₂] (8). Compacted pellets of 7 and 8 show conductivities of 2 × 10^-7 and 3 × 10^-5 S cm^-1 at room temperature. The structure of NBu₄-[Au₂(C₃S₅) (CH₂PPh₂CH₂)] (1a) has been established by an X-ray diffraction study and shows a nine-membered diauracycle with an Au...Au distance of 3.026(1) A.