Reactions of trans-[RuCl2(CO)2(PEt3)2]with 1,1-dithiolates:: Stepwise formation of cis-[Ru(CO)(PEt3)(S2X)] (X = CNMe2, CNEt2, COEt, P(OEt)2, PPh2)

Traps-[RuCl2(CO)(2)(PEt3)(2)] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes, cis-[Ru(CO)(PEt3)(S2X)(2)] (X = CNMe2, CNEt2, COEt, P(OEt)(2), PPh2). Two intermediates have been isolated; trans-[Ru(PEt3)(2)Cl-(CO){S2P(OEt)(2)}] and trans-[Ru(PEt3)(2)(CO)(eta(1)-S2COEt)(eta(2)-S2COEt)], allowing a simple reaction scheme to be postulated involving three steps; (i) initial replacement of cis carbonyl and chloride ligands, (ii) substitution of the second chloride, (iii) loss of a phosphine. Thermolysis of cis-[Ru(CO)(PEt3)(S2CNMe2)(2)] with Ru-3(CO)(12) in xylene affords trinuclear [Ru-3(mu(3)-S)(2)(PEt3)(CO)(8)] as a result of dithiocarbamate degradation. Crystal structures of cis-[Ru(CO)(PEt3)(S2X)(2)] (X = NMe2, COEt), trans-[Ru(PEt3)(2)Cl(CO){S2P(OEt)(2)}], trans[Ru(PEt3)(2)(CO)(eta(1)-S2COEt)(eta(2)-S2COEt)] and [Ru-3(mu(3)-S)(2)(PEt3)(CO)(8)] are reported. (c) 2005 Elsevier B.V. All rights reserved.