Reactions of trans-[RuCl 2(CO) 2(PEt 3) 2] with 1,1-dithiolates: Stepwise formation of cis-[Ru(CO)(PEt 3)(S 2X)] (X = CNMe 2, CNEt 2, COEt, P(OEt) 2, PPh 2)

Abstract

Trans-[RuCl 2(CO) 2(PEt 3) 2] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes, cis-[Ru(CO)(PEt 3)(S 2X) 2] (X = CNMe 2, CNEt 2, COEt, P(OEt) 2, PPh 2). Two intermediates have been isolated; trans-[Ru(PEt 3) 2Cl(CO){S 2P(OEt) 2}] and trans-[Ru(PEt 3) 2(CO)(η 1-S 2COEt)(η 2-S 2COEt)], 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)(PEt 3)(S 2CNMe 2) 2] with Ru 3(CO) 12 in xylene affords trinuclear [Ru 3(μ 3-S) 2(PEt 3)(CO) 8] as a result of dithiocarbamate degradation. Crystal structures of cis-[Ru(CO)(PEt 3)(S 2X) 2] (X = NMe 2, COEt), trans-[Ru(PEt 3) 2Cl(CO){S 2P(OEt) 2}], trans-[Ru(PEt 3) 2(CO)(η 1-S 2COEt)(η 2-S 2COEt)] and [Ru 3(μ 3-S) 2(PEt 3)(CO) 8] are reported.