Ruthenium -, dichloride

Other ruthenium-based catalysts are also active. Ruthenium dichloride-cymene complex is stereoselective for formation of the Z-vinyl silanes from terminal alkynes. 

While ruthenium dichlorides always showed an undesirable initiation time, these novel catalysts start the reaction without delay. For compounds not containing functional groups their turnover frequencies can be several thousands per hour, but for polar molecules the total turnover may be as low as fifty, obtained in several hours. 

Figure 1.6 Metathesis Catalysts (22) Phenylmethylene-bis-(tricyclohexyl-phosphine) ruthenium dichloride (I), (IMesH2)(PCy3)(Cl)2Ru=CHPh (III)...

Norbornene polymers or polymers from dicyclopentadiene, respectively, may be formed by the interaction of a cyclic olefin with a ROMP catalyst. Increased reinforcement density provides for extremely high stiffness and strength in poly(norbornene) composites. As catalyst, Phenylmethylene-bis-(tricyclohexylphosphine) ruthenium dichloride is used (30). 

Ruthenium complexes have been described that are active both in the ROMP reaction and in a subsequent hydrogenation step (30). These catalysts have the pyrimidin moiety incorporated, for example, (l,3-diisopropyltetrahydropyrimidin-2-ylidene) (ethoxy-methylene) (tricyclohexylphosphine) ruthenium dichloride. 

They can be handled analogous to thermosetting resins, and thus the use of highly volatile comonomers, such as ethene or prop-ene is prohibitive. Instead, other vinyl monomers are used. A heat curable formulation uses a mixture of tetracyclododecene, 2-norbomene, 5-vinyl-2-norbomene, and divinylbenzene as reactive components (41). The mixture further contains 3,5-di-ferf-butylhy-droxyanisole as antioxidant and a hybrid catalyst system containing a zirconium based metathesis catalyst and a radical catalyst. The metathesis catalyst is benzylidene (l,3-dimesitylimidazolidin-2-yl-idene)(tricyclohexylphosphine)ruthenium dichloride and the radical catalyst is di-ferf-butyl peroxide. 

The latter, on reaction with methylamine yielded via the P-epoxide 373, the trans-a aminoalcohol 374, which was N-acylated to the amide 375. Acid-catalysed dehydration of the tertiary alcohol 375, led to the olefin 375, from which the key radical precursor, the chlorothioether377 was secured in quantitative yield by reaction with N-chlorosuccinimide. In keeping with the earlier results recorded for structurally related compounds, 377 on heating in the presence of ruthenium dichloride and triphenylphosphine also underwent a 5-exo radical addition to generate the cyclohexyl radical 378 which recaptured the chlorine atom to furnish the a-chloro-c/5-hydroindolone 379. Oxidation of thioether 379 gave the corresponding sulfoxide 380, which on successive treatment with trifluoroacetic anhydride and aqueous bicarbonate led to the chloro-a-ketoamide 381. The olefin 382 resulting from base induced dehydrochlorination of 381, was reduced to the hydroxy-amine 383, which was obtained as the sole diastereoisomer... 

Bis(ruthenium dichloride-S-BINAP)-triethylamine catalyst Ruthenium, bis[[1,1l-binaphthalene]-2,2 -diylbis[diphenylphosphine]-P,P ]di-p-chlorodichloro(N,N-diethylethanamine)di- (114717-51-0), 77, 3... 

Ruthenium Dichloride, RuCL, was stated by Claus4 to result w hen chlorine is passed over heated ruthenium. Repetition of the experiment by Gutbier and Trenkner5 in 1905 led to no definite result, varying amounts of chlorine being absorbed, but always considerably less than theory requires for the dichloride. The experiments w7ere by no means exhaustive, and do not justify the assumption that the dichloride cannot be prepared in this way. As Gutbier points out, it is quite possible that a reversible reaction takes place between the ruthenium and chlorine, thus ... 

Ruthenium combines with oxygen in several different proportions. A monoxide, RuO, was stated by Claus 6 to result when the diehloride, RuC12, is heated with slightly more than one equivalent of sodium carbonate in a current of carbon dioxide. This result was apparently accepted until 1905, in which year Gutbier and Trenkner,7 as has already been mentioned, threw doubt on the supposed existence of ruthenium dichloride. This raised the question as to whether or not the monoxide could exist. Experiments carried out by Gutbier and Jtansohoff with a chloride of ruthenium and sodium carbonate after the maimer described by Claus gave very uncertain results, from which it may be concluded that ruthenium monoxide has not as yet been prepared, and is possibly incapable of a separate existence. The... 

Ru(CN)2 was prepared in 1920 by addition of KCN to the blue ruthenium dichloride solution.20 No structural information is available on the material. K4[Ru(CN)6] was first made in 1896 either by the action of KCN on K2[Ru04] or by boiling a solution of RuC13 with an excess of KCN until the solution loses its colour.21 As described elsewhere,2 various other metal salts of this anion have been prepared together with the anhydrous free acid H4[Ru(CN)6] and in several earlier studies, the electronic, IR and Raman spectra22 have been recorded and assignments proposed. The IR spectra of solid Y4[Ru(CN)6] (Y = H, D) have been measured and interpreted as showing unsymmetrical (N—Y- -N) bonds.23 The "Ru NMR spectrum of K4[Ru(CN)6] has been recorded.24... 

Week [4] prepared photoluminescent polynorborene derivatives, (VII), by polymerizing aluminum-8-hydroxyquinoline-functionalized norborene, (VI), using benzylidene (l,3-dimesitylimidazolydin-2-ylidene)-(tricyclohexylpho-sphine)ruthenium dichloride. 

The catalyst solution was prepared by adding ruthenium dichloride((S)-(6,6 -dimethoxybiphenyl-2,2 -di-yl)bis[bis(3,5-diisopropyl-phenyl)phosphine])[(R,R)-2-diphenylethylenediamine)] (0.050 mmol) to 20 ml iso-propyl alcohol and the mixture stirred 20 minutes at ambient temperature and stored. 

Bis(tricyclohexylphosphine)benzylidine ruthenium dichloride was obtained from Strem Chemical Company and used as received. 

A new probe of solvent accessibility of bound sensitizers has been described and tested for the particular case of a series of Ru" and Os photosensitizers bound to sodium lauryl sulphate micelles. The method depends upon the large solvent deuterium effect on excited-state lifetimes, and a correlation has been established between accessibility of bound complexes and hydrophobicity of the ligands. Luminescence properties of amphiphilic annelide-type complexes of ruthenium in micellar phases have been described. In the case of [4,4 -bis(nonadecyl)-2,2 -bipyridyl]bis-[4,4 -di-(10,13,16-trioxaundecyl)-2,2 -bipyridyl]ruthenium dichloride, intramicellar self-quenching effects have an influence on the excited-state lifetime, and the mechanism of self-quenching has been determined. Deactivation of [Ru(bipy)3] by [Co(EDTA)] has been studied in a micellar environment and found to occur by electron transfer at diffusion-controlled rates a stereoselective effect has been observed. ... 

Bis(trimethylsilyl) peroxide, (CH3)3SiOOSi(CH3)3, is prepared from trimethylsilyl chloride, l,4-diaza[2,2,2]bicyclooctane, and Dabco s complex with 2 mol of hydrogen peroxide [127]. It is used alone [228] or in the presence of catalysts such as pyridinium dichromate [236] trimethylsilyl trifluoromethanesulfonate, CF3S03Si(CH3)3 [228, 237] or tris-(triphenylphosphine)ruthenium dichloride, [(C6H5)3P]3RuCl2 [236]. This reagent oxidizes primary alcohols to aldehydes (in preference to the oxidation of secondary alcohols to ketones [236]), ketones to esters or lactones Baeyer-Villiger reaction) [238], and nucleoside phosphites to phosphates [228]. All these oxidations require anhydrous conditions. 

Whereas internal acetylenes are oxidized to a-diketones, terminal acetylenes give carboxylic acids with one less carbon on treatment with thallium trinitrate [413], potassium permanganate [843], iodosobenzene with tris(triphenylphosphine)ruthenium dichloride as a catalyst [787], or a rather rare oxidant, pentafluoroiodobenzene bis(trifluoroacetate) [797] (equation 144). 

Alkyl acetylenyl ethers treated with iodosobenzene in dichloromethane in the presence of 1% of tris(triphenylphosphine)ruthenium dichloride for 15 min at room temperature furnish keto esters in 59-70% yields (equation 335) [786]. 

The unusual oxidant nickel peroxide converts aromatic aldehydes into carboxylic acids at 30-60 °C after 1.5-3 h in 58-100% yields [934. The oxidation of aldehydes to acids by pure ruthenium tetroxide results in very low yields [940. On the contrary, potassium ruthenate, prepared in situ from ruthenium trichloride and potassium persulfate in water and used in catalytic amounts, leads to a 99% yield of m-nitrobenzoic acid at room temperature after 2 h. Another oxidant, iodosobenzene in the presence of tris(triphenylphosphine)ruthenium dichloride, converts benzaldehyde into benzoic acid in 96% yield at room temperature [785]. The same reaction with a 91% yield is accomplished by treatment of benzaldehyde with osmium tetroxide as a catalyst and cumene hydroperoxide as a reoxidant [1163]. 

The polymeric form of benzene ruthenium dichloride has catalytic behavior similar to Ru(PPh3)3Cl2 in the hydrogenation of olefins (332). Similar catalytic activity has been observed for the dimer [(CgHg)-RuCl2]2 in dimethylformamide solution. On the basis of kinetic studies. 

Tristtriphenylptosphine (ruthenium dichloride, [(C6H,)3P]3RuCl2. Mol. wt. 959.44. Supplier Strem. 

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