858524-27-3Relevant academic research and scientific papers
σ-Organyl complexes of ruthenium and osmium supported by a mixed-donor ligand
Wilton-Ely, James D. E. T.,Honarkhah, Sanaz J.,Wang, Ming,Tocher, Derek A.,Slawin, Alexandra M. Z.
, p. 1930 - 1939 (2005)
A series of vinyl, aryl, acetylide and silyl complexes [Ru(R) (κ2-MI)(CO)(PPh3)2] (R = CH=CH 2, CH=CHPh, CH=CHC6H4CH3-4, CH=CHtBu, CH=CHCPh2OH, C(C≡CPh)=CHPh, C 6H5, C≡CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh 3)2] or [Ru(R)Cl(CO)(BTD)(PPh3)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)(κ2-MI)(CO)(PPh3)2] was prepared from [Os(CH=CHPh)(CO)Cl(BTD)(PPh3)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 6H9)(κ2-MI)(CO)(PPh3) 2]. Dehydration of the complex [Ru(CH=CH-CPh2OH) (κ2-MI)(CO)(PPh3)2] with HBF4 yielded the vinyl carbene [Ru(=CHCH=CPh2)(κ2-MI)(CO) (PPh3)2]BF4. The hydride complexes [MH(κ2-MI)(CO)(PPh3)2] (M = Ru, Os) were obtained from the reaction of HMI and KOH with [RuHCl(CO)(PPh3) 3] and [OsHCl(CO)(BTD)(PPh3)2], respectively. Reaction of [Ru(CH=CHC6H4CH3-4) (κ2-MI)(CO)(PPh3)2] with excess HC≡CPh leads to isolation of the acetylide complex [Ru(C≡CPh) (κ2-MI)(CO)(PPh3)2], which is also accessible by direct reaction of [Ru(C≡CPh)Cl(CO)(BTD)(PPh 3)2] with 1-methyl-2-mercaptoimidazole and NaOMe. The thiocarbonyl complex [Ru(CPh=CHPh)Cl(CS)(PPh3)2] reacted with HMI and NaOMe without migration to yield [Ru(CPh=CHPh)(κ2- MI)(CS)(PPh3)2], while treatment of [Ru(CH=CHPh)Cl(CO) 2(PPh3)2] with HMI yielded the monodentate acyl product [Ru{η1-C(=O)CH=CHPh}(κ2-MI)(CO) (PPh3)2]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported. The Royal Society of Chemistry 2005.
