SYNTHESIS AND REACTIVITY OF TRINUCLEAR GOLD(III) DITHIOLATE COMPLEXES - X-RAY STRUCTURE OF [AU(C6F5)(S2C6H4)](3) AND [AU(C6F5)(S2C6H4)(SC(6)H(4)SPPH(3))]

Q(2)[Zn(S-S)(2)] or [SnMe(2)(S-S)] (Q = NBu(4) or PPN, S-S = S2C6H4, S2C6H3CH3, or C3S5 (dmit)) reacts with trans-[Au(C6F5)Cl-2(tht)] affording trinuclear species [Au(C6F5)(S-S)](3) (1-3). When [AuX(3)(tht)] (X = Cl or Br) are used instead, [AuBr(S-S)], (4-6) and [AuCl(dmit)](n) (7) are obtained. Complex 1 further reacts with PPh(3) to give [Au(C6F5)(S2C6H4)(SC(6)H(4)SPPh(3))]. Complexes 1-3 react with neutral (pyridine) or anionic (Cl, Br, or SCN) ligands affording [Au(C6F5)(S-S)(py)] (9a-c) or Q[Au(C6F5)(S-S)X] (10a-c-12a-c) complexes. The structures of 1 and 8 have been established by X-ray crystallography. Complex 1 shows a six-membered Au3S3 ring which adopts a chair configuration and shows a gold-gold distance of 3.515 Angstrom. Complex 8 is a mononuclear square-planar gold(III) complex with a new SC(6)H(4)SPPh(3) thiolate ligand, the P-S bond length being 2.058(5) Angstrom.