The Effect of N-Donor Ligands on the Reaction of Ruthenium Hydrides with 1-Alkynes

Santos, Aurora; López, Javier; Galán, Amalia; González, J. J.; Tinoco, Pilar; Echavarren, Antonio M.

doi:10.1021/om970054q

Cited by 35 publications

(16 citation statements)

References 16 publications

(19 reference statements)

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“…Our previous work 8c and that of others 18, 19 has shown an acetylide ligand can be generated by heating vinyl species with excess alkyne. Thus, heating [Ru(CH=CHC 6 H 4 Me-4)(j 2 -MI)(CO)(PPh 3 ) 2 ] (4) with excess phenylacetylene in 1,2dichloroethane yielded the acetylide complex [Ru(C≡CPh)(j 2 -MI)(CO)(PPh 3 ) 2 ] ( 14) by a second route.…”

Section: Complexes Bearing R-organyl and R-silyl Ligandsmentioning

confidence: 89%

“…8c,d However, typically these ligands have contained just one type of donor element (O, S or N). Bidentate examples include carboxylate, 12 xanthate 13 dithiocarbamate, 13,14 S 2 CPCy 3 , 15 alkenyldithiocarboxylate, 16 alkynyldithiocarboxylate, 17 dihydrobispyrazolylborate, 8a amidine, 18 phenanthroline 19 and bipyridyl 19 ligands. Our current work explores the reactivity of vinyl complexes with mixed-donor bidentate ligands and the effect of these chelates on subsequent functional group transformations.…”

Section: Introductionmentioning

confidence: 99%

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σ-Organyl complexes of ruthenium and osmium supported by a mixed-donor ligand

et al. 2005

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A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa2-MI)(CO)(PPh3)2] (R = CH=CH2, CH=CHPh, CH=CHC6H4CH3-4, CH=CH(t)Bu, CH=2OH, C(C triple bond CPh)=CHPh, C6H5, C triple bond CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh3)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)(kappa2-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)(PPh3)2] and subsequent addition of the HMI ligand and excess sodium methoxide yielded the dehydrated 1,3-dienyl complex [Ru(CH=CHC6H9)(kappa2-MI)(CO)(PPh3)2]. Dehydration of the complex [Ru(CH=CHCPh2OH)(kappa2-MI)(CO)(PPh3)2] with HBF4 yielded the vinyl carbene [Ru(=CHCH=CPh2)(kappa2-MI)(CO)(PPh3)2]BF4. The hydride complexes [MH(kappa2-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)(kappa2-MI)(CO)(PPh3)2] with excess HC triple bond CPh leads to isolation of the acetylide complex [Ru(C triple bond CPh)(kappa2-MI)(CO)(PPh3)2], which is also accessible by direct reaction of [Ru(C triple bond CPh)Cl(CO)(BTD)(PPh3)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)(kappa2-MI)(CS)(PPh3)2], while treatment of [Ru(CH=CHPh)Cl(CO)2(PPh3)2] with HMI yielded the monodentate acyl product [Ru{eta(1)-C(=O)CH=CHPh}(kappa2-MI)(CO)(PPh3)2]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported.

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Section: Complexes Bearing R-organyl and R-silyl Ligandsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

σ-Organyl complexes of ruthenium and osmium supported by a mixed-donor ligand

et al. 2005

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“…The C=O stretching frequencies were found between 1952 and 1941 cm –1 ; the Ru–H stretching vibrations could not be assigned. They are reported in the literature to appear at 1980–1950 cm –1 ,12,17a,21 which is close to the intense C=O absorption, or to be unobservable because of their low intensities 22. The 31 P{ 1 H} NMR resonances of 9a , b ( δ = 46.3, 46.4 ppm) and 10a , b ( δ = 44.9, 43.9 ppm) are shifted by about 50 ppm downfield with respect to those of free triphenylphosphane.…”

Section: Resultsmentioning

confidence: 88%

Ruthenium Complexes Bearing N–H Acidic Pyrazole Ligands

et al. 2010

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Chelate ligands containing at least one pyrazole group were treated with RuCl2(PPh3)3, RuHCl(CO)(PPh3)3 and RuH2(CO)(PPh3)3 to form ruthenium complexes bearing protic N–H groups in close proximity to the catalytically active ruthenium centre. In the case of the hydridoruthenium complex RuHCl(CO)(PPh3)3 the resulting complexes also contain abasic hydrido ligand. The combination of acidic and basic hydrogen species in one molecule and the arising two‐site reactivity was thoroughly investigated spectroscopically and by DFT calculations. Catalytic tests on the hydrogenation and transfer hydrogenation of acetophenone showed a general activity of these systems.

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“…Both of these features were found to be at values shifted compared to those in the precursors. 18 suggests that the bpy unit remains uncoordinated to the ruthenium centre. The overall composition was confirmed by mass spectrometry and elemental analysis.…”

Section: Resultsmentioning

confidence: 99%