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)

Trans-[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)2Cl(CO){S2P(OEt)2}] and trans-[Ru(PEt3)2(CO)(η1-S2COEt)(η2-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 Ru3(CO)12 in xylene affords trinuclear [Ru3(μ3-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)2Cl(CO){S2P(OEt)2}], trans-[Ru(PEt3)2(CO)(η1-S2COEt)(η2-S2COEt)] and [Ru3(μ3-S)2(PEt3)(CO)8] are reported.