Synthesis and reactivity of trinuclear gold(III) dithiolate complexes. X-ray structure of [Au(C6F5)(S2C6H4)]3 and [Au(C6F5)(S2C6H4)(SC6H4SPPh3)].

Q2[Zn(S-S)2] or [SnMe2(S-S)] (Q = NBu4 or PPN, S-S = S2C6H4, S2C6H3CH3, or C3S5 (dmit)) reacts with trans-[Au(C6F5)Cl2(tht)] affording trinuclear species [Au(C6F5)(S-S)]3 (1-3). When [AuX3(tht)] (X = Cl or Br) are used instead, [AuBr(S-S)]n (4-6) and [AuCl(dmit)]n (7) are obtained. Complex 1 further reacts with PPh3 to give [Au(C6F5)(S2C6H4)(SC 6H4SPPh3)]. 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 Å. Complex 8 is a mononuclear square-planar gold(III) complex with a new SC6H4SPPh3 thiolate ligand, the P-S bond length being 2.058(5) Å. © 1995 American Chemical Society