Sigma-organyl complexes of ruthenium and osmium supported by a mixed-donor ligand.
A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa(2)-MI)(CO)(PPh(3))(2)](R = CH=CH(2), CH=CHPh, CH=CHC(6)H(4)CH(3)-4, CH=CH(t)Bu, CH=(2)OH, C(C triple bond CPh)=CHPh, C(6)H(5), Ctriple bond CPh, SiMe(2)OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh(3))(2)] or [Ru(R)Cl(CO)(BTD)(PPh(3))(2)](BTD = 2,1,3-benzothiadiazole) by reaction with the nitrogen-sulfur mixed-donor ligand, 1-methyl-2-mercaptoimidazole ( HMI), in the presence of base. In the same manner, [Os(CH=CHPh)(kappa(2)-MI)(CO)(PPh(3))(2)] was prepared from [Os(CH=CHPh)(CO)Cl(BTD)(PPh(3))(2)]. The in situ hydroruthenation of 1-ethynylcyclohexan-1-ol by [RuH(CO)Cl(BTD)(PPh(3))(2)] and subsequent addition of the HMI ligand and excess sodium methoxide yielded the dehydrated 1,3-dienyl complex [Ru(CH=CHC(6)H(9))(kappa(2)-MI)(CO)(PPh(3))(2)]. Dehydration of the complex [Ru(CH=CHCPh(2)OH)(kappa(2)-MI)(CO)(PPh(3))(2)] with HBF(4) yielded the vinyl carbene [Ru(=CHCH=CPh(2))(kappa(2)-MI)(CO)(PPh(3))(2)]BF(4). The hydride complexes [MH(kappa(2)-MI)(CO)(PPh(3))(2)](M = Ru, Os) were obtained from the reaction of HMI and KOH with [RuHCl(CO)(PPh(3))(3)] and [OsHCl(CO)(BTD)(PPh(3))(2)], respectively. Reaction of [Ru(CH=CHC(6)H(4)CH(3)-4)(kappa(2)-MI)(CO)(PPh(3))(2)] with excess HC triple bond CPh leads to isolation of the acetylide complex [Ru(C triple bond CPh)(kappa(2)-MI)(CO)(PPh(3))(2)], which is also accessible by direct reaction of [Ru(C triple bond CPh)Cl(CO)(BTD)(PPh(3))(2)] with 1-methyl-2-mercaptoimidazole and NaOMe. The thiocarbonyl complex [Ru(CPh = CHPh)Cl(CS)(PPh(3))(2)] reacted with HMI and NaOMe without migration to yield [Ru(CPh= CHPh)(kappa(2)-MI)(CS)(PPh(3))(2)], while treatment of [Ru(CH=CHPh)Cl(CO)(2)(PPh(3))(2)] with HMI yielded the monodentate acyl product [Ru{eta(1)-C(=O)CH=CHPh}(kappa(2)-MI)(CO)(PPh(3))(2)]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported.[1]References
- Sigma-organyl complexes of ruthenium and osmium supported by a mixed-donor ligand. Wilton-Ely, J.D., Honarkhah, S.J., Wang, M., Tocher, D.A., Slawin, A.M. Dalton transactions (Cambridge, England : 2003) (2005) [Pubmed]
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