1000398-38-8Relevant articles and documents
Synthesis and reactions of five-coordinate mono- and binuclear thiocarbonyl - alkenyl and thioacyl complexes of ruthenium(II)
Cowley, Andrew R.,Hector, Andrew L.,Hiil, Anthony F.,White, Andrew J. P.,Williams, David J.,Wilton-Ely, James D. E. T.
, p. 6114 - 6125 (2008/10/09)
The reactions of [RuHCl(CS)(PPh3)3] with R 1C≡CR2 (R1 = R2 = H, Ph, CO2Me; R1 = H, R2 = C6H 4Me-4; R1 = C≡CPh, R2 = Ph) lead to the five- or six-coordinate (R1 = R2 = CO2Me) σ-alkenyl complexes [Ru(CR1=CHR2)Cl(CS)(PPh 3)2], the stilbenyl derivative being also formed by thermolysis of [RuCl(κ2-O2CH)(CS)(PPh 3)2j in the presence of diphenylacetylene. These complexes rapidly react with carbon monoxide to provide the bidentate thioacyl complexes [Ru(η2-SCCR1=CHR2)Cl(CO)(PPh 3)2] (R1 = R2 = H, Ph; R1 = H, R2 = Ph; R1 = C≡CPh, R2 = Ph) or the σ-alkenyl tautomer [Ru(CR1= CHR2)Cl(CO)(CS) (PPh3)2] (R1 = R2 = CO 2Me), depending on the alkenyl substituent. The compound [RuHCl(CS)(PPh3)3] reacts with 1/2 equiv of 1,4-diethynylbenzene to provide the coordinatively unsaturated bimetallic species [(Ph3P)2(SC)ClRu(CH=CHC6H 4CH=CH)RuCl(CS)(PPh3)2] in situ, which undergoes migratory insertion on addition of carbon monoxide to give the bis(thioacyl) species [(Ph3P)2(OC)ClRu-(η2- SCCH=CHC6H4CH=CHCS-η2)RuCl(CO)(PPh 3)2]. On reaction with BSD (2,1,3-benzoselenadiazole), [Ru(CH=CH2)Cl(CS)(PPh3)2] gives [Ru(CH=CH 2)Cl(CS)(BSD)(PPh3)2] without migration of the alkenyl group. The complex [RuHCl(CS)(BSD)(PPh3)2] results from the reaction of [RuHCl(CS)(PPh3)3] and BSD, and this complex hydroruthenates alkynes cleanly to provide [Ru(CR1=CHR 2)Cl(CS)(BSD)(PPh3)2], carbonylation of which leads to loss of BSD and formation of [Ru(η2-SCCR 1=CHR2)Cl(CO)(PPh3)2]. Addition of carboxylate donors R′CO2_ (R′ = H, Fc) to the complexes [RuRCl(CS)(PPh3)2] (R = CH=CH2, C(C≡CPh)=CHPh) results in the complexes [RuR(κ2-O 2CR′)(CS)(PPh3)2], without migratory insertion. A trimetallic example, Fe[C5H4CO 2Ru{C(C≡CPh)=CHPh}(CS)(PPh3)2] 2, was formed in the corresponding reaction with 1,1′- ferrocenedicarboxylic acid and Et3N. The crystal structures of the complexes [Ru(CPh=CHPh)Cl(CS)(PPh3)2], [Ru{C(C≡CPh)=CHPh}Cl(CS)(PPh3)2], [Ru{η2-SCC-(C≡CPh)=CHPh}Cl(CO)(PPh3) 2], [Ru{C(C≡CPh)=CHPh}(κ2-O 2CFc)(CS)(PPh3)2] and Fe[C5H 4CO2-Ru{C(C≡CPh)=CHPh}(CS)(PPh3) 2]2 are reported.
