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Dichlorotris(triphenylphosphine)ruthenium(II)
About: Dichlorotris(triphenylphosphine)ruthenium(II) is a research topic. Over the lifetime, 35 publications have been published within this topic receiving 3489 citations.
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TL;DR: In this article, the reduction of dichlorotris(triphenylphosphine) ruthenium(II) in tetrahydrofuran-acetonitrile by sodium or magnesium amalgam produces a compound shown to be a hydrido ortho-metallated phosphine ruthensium (II) complex RuH(C6H4PPh2)(MeCN)(PPh3)2.
Abstract: The reduction of dichlorotris(triphenylphosphine)ruthenium(II) in tetrahydrofuran–acetonitrile by sodium or magnesium amalgam produces a compound shown to be a hydrido ortho-metallated phosphine ruthenium(II) complex RuH(C6H4PPh2)(MeCN)(PPh3)2. This compound has all the characteristics of a complex previously reported and alleged to be a ruthenium(0) complex containing a π-bonded acetonitrile ‘Ru(MeCN)(PPh3)4·MeCN’.Detailed study of the system shows that there are labile intermediates, Ru(MeCN)2(PPh3)2 which is paramagnetic, Ru(MeCN)3(PPh3)2, and Ru(MeCN)(PPh3)3. The reduction in pyridine gives two isomers of RuH(C6H4PPh2)(C5H5N)(PPh3)2 while in the presence of 2,2′-bipyridyl the main product is a purple complex RuH(C6H4PPh2)(bipy)(PPh3). In styrene the known complex Ru(styrene)2(PPh3)2 is obtained.Reactions of the ruthenium(II) species RuH(C6H4PPh2)(MeCN)(PPh3)2 with propene and water are reported.The various compounds have been characterised by i.r. and 1H and 31P n.m.r. spectroscopy.It is concluded that reductions of RuCl2(PPh3)3 or 4 lead to the abstraction of hydride from the solvent if no strongly co-ordinating ligand is present. In the presence of co-ordinating ligands, species containing ortho-metallated triphenylphosphine groups are formed via intramolecular oxidative addition of a C–H bond to transient ruthenium(0) intermediates.
TL;DR: In the presence of dichlorotris(triphenylphosphine)ruthenium(II) p-toluenesulfonyl chloride was found to react with styrenes under mild reaction conditions to give alkenyl sulfones in good yields as discussed by the authors.
Abstract: In the presence of dichlorotris(triphenylphosphine)ruthenium(II) p-toluenesulfonyl chloride was found to react with styrenes under mild reaction conditions to give alkenyl sulfones in good yields. The reaction was highly regio- and stereoselective and formed only β-hydrogen-substituted (E)-isomers.
01 Dec 1985
TL;DR: The use of transition metal complexes as catalysts for the reduction of the heteroatom containing ring in polynuclear heteroaromatic compounds has been investigated in this paper, where the ability of a substrate to bind to the catalyst has been found to be a primary factor in determining reduction rates.
Abstract: The use of transition metal complexes as catalysts for the reduction of the heteroatom containing ring in polynuclear heteroaromatic compounds has been investigated. Additionally, a study has been made of the heterogeneously catalyzed cleavage of carbon-nitrogen bonds in the regioselectively reduced compound, 1,2,3,4-tetrahydroquinoline. Chlorotris(triphenylphosphine)rhodium(I) (both homogeneous and polymer-supported), dichlorotris-(triphenylphosphine)ruthenium(II) and dicarbonyldichloro-bis(triphenylphosphine)ruthenium(II) have been used as catalysts for the selective reductions of a variety of compounds, including: quinoline, 5,6-benzoquinoline, 7,8-benzoquinoline, acridine, phenanthridine, indole and benzothiophene. Both molecular hydrogen and easily dehydrogenated saturated nitrogen aromatics have been used as hydrogen sources. The rates of reduction of single compounds and various mixtures of compounds have been determined. The ability of a substrate to bind to the catalyst has been found to be a primary factor in determining reduction rates. Deuterium gas has been substituted for hydrogen gas in the reduction of quinoline and phenanthridine. The deuterium incorporation into the products was examined by /sup 1/H NMR and mass spectroscopy. These results indicate that the reduction of quinoline is a two step process, a reversible hydrogenation of the 1-2 carbon-nitrogen bond followed by an irreversible reduction of the 3-4 carbon-carbon bond. Mixtures of quinoline and chlorotris(triphenylphosphine)rhodium(I), in the presence and absence of hydrogen, havemore » been examined by /sup 31/P NMR. Several quinoline rhodium complexes have been identified in these mixtures. Various heterogeneous catalysts have been investigated for the cleavage of the carbon-nitrogen bonds in 1,2,3,4-tetrahydroquinoline. Two highly loaded nickel on silica catalysts have proven to be active for this reaction. 93 refs., 43 figs., 38 tabs.« less