Nine- and ten-membered diauracycles with the C3S52- ligand, crystal structure of NBu(4)[Au-2(mu-C3S5)(mu-CH(2)PPh(2)CH(2))]

The synthesis of hetero-bridged dinuclear gold(I) complexes with the C3S52-(1,3-dithiole-2-thione-4,5-dithiolate) ligand has been tested by different methods: (i) reaction of [Au(mu-L-L)X(2)](n-) with Na2C3S5 ethanolic solutions; (ii) reaction of [Au-2(C3S5)(mu AsPh(3))](n) with different bidentate ligands. The resulting complexes Q[Au-2(mu-C3S5)(mu-CH(2)PPh(2)CH(2))] (1), [Au-2(mu-C3S5)(mu-dppe)] (2) and Q[Au-2(C3S5)(S(2)CNR(2))] (R = Me (3), Et (4) or CH(2)Ph (5)) have been characterized by analysis, conductivity, IR, P-31 and H-1 NMR. Complex (PPN)(2)[Au(C3S5)(2)] (6) (PPN = N(PPh(3))(2)) has been achieved by reaction of [AuCl(tht)] (tht = tetrahydrothiophene) or [AuCl(AsPh(3))] with Na2C3S5 and addition of (PPN)Cl. Reaction of 1 with (TTF)(3)(BF4)(2) (TTF = tetrathiafulvalene) affords (TTF) [Au-2(C3S5)(CH(2)PPh(2)CH(2))] (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 x 10(-7) and 3 x 10(-5) S cm(-1) at room temperature. The structure of NBu(4)-[Au-2(C3S5)(CH(2)PPh(2)CH(2))] (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) Angstrom.