Synthesis and reactivity of trinuclear gold(III) dithiolate complexes. X-ray structure of [Au(C6F5)(S2C6H4)] 3 and [Au(C6F5)(S2C6H4)(SC 6H4SPPh3)]

Article abstract of DOI:10.1021/om00012a021

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 ?. 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) ?.