Ruthenium carbon dioxide

Since the reverse reaction proceeds by the removal of COj from solution as Li2C03 precipitation, the interconversion of the ruthenium M-CO2 and M-CO could be regarded as very shifted equilibrium. We have already reported that these ruthenium carbon dioxide and carbonyl complexes are in an acid-base equilibria (eq. 7). 

Syntheses from Dry Metals and Salts. Only metaUic nickel and iron react direcdy with CO at moderate pressure and temperatures to form metal carbonyls. A report has claimed the synthesis of Co2(CO)g in 99% yield from cobalt metal and CO at high temperatures and pressures (91,92). The CO has to be absolutely free of oxygen and carbon dioxide or the yield is drastically reduced. Two patents report the formation of carbonyls from molybdenum and tungsten metal (93,94). Ruthenium and osmium do not react with CO even under drastic conditions (95,96). 

Ruthenium is a known active catalyst for the hydrogenation of carbon monoxide to hydrocarbons (the Fischer-Tropsch synthesis). It was shown that on rathenized electrodes, methane can form in the electroreduction of carbon dioxide as weU. At temperatures of 45 to 80°C in acidihed solutions of Na2S04 (pH 3 to 4), faradaic yields for methane formation up to 40% were reported. On a molybdenium electrode in a similar solution, a yield of 50% for methanol formation was observed, but the yield dropped sharply during electrolysis, due to progressive poisoning of the electrode. 

The sensor for the measurement of high levels of CO2 in gas phase was developed, as well90. It was based on fluorescence resonance energy transfer between 0 long-lifetime ruthenium polypyridyl complex and the pH-active disazo dye Sudan III. The donor luminophore and the acceptor dye were both immobilized in a hydrophobic silica sol-gel/ethyl cellulose hybrid matrix. The sensor exhibited a fast and reversible response to carbon dioxide over a wide range of concentrations. 

Carbon Monoxide Reduction at Ruthenium. Carbon monoxide can be reduced to both methane and methanol under conditions nearly identical to those for the reduction of carbon dioxide (Table I, All experiments, using one electrode, are presented in the order they were performed). 

Methanol Reduction at Ruthenium. The reduction of methanol to methane does occur as shown by the data in Table III. The data for each electrode are presented in the order that they were collected. Rates can be higher for methanol reduction compared to carbon dioxide reduction though faradaic efficiencies are lower. Unlike carbon dioxide reduction, the rate of methane formation is extremely... 

Keywords Asymmetric Hydrogenation m Carbon Dioxide m Carbonylation m Dimethylformamide Enantioselectivity m Formic Acid m Homogeneous Hydrogenation n Palladium Catalysts Radical Reactions m Ruthenium Catalysts m Supercritical Fluids m Solvent Replacement... 

The formation of carbido-carbonyl cluster compounds with ruthenium and osmium appears to be common in pyrolysis reactions the basic reaction may be viewed as the transformation of the coordinated carbon monoxide to carbide and carbon dioxide. Small variations in... 

Primary aliphatic or aromatic amines RNH2 are converted into carbamates RNHCC Et on treatment with carbon monoxide and di-t-butyl peroxide in the presence of palladium(II) chloride and copper(II) chloride357. Carbamic esters 304 and 305 are also obtained from aliphatic amines and ortho carbonates (R30)4C358. Vinyl carbamates R12NC02CH=CHR2 are produced from secondary aliphatic amines, acetylenes R2C=CH (R2 = Bu or Ph) and carbon dioxide in the presence of ruthenium(III) chloride359. 

G. Orellana, M. C. Moreno-Bondi, E. Segovia, M. D. Marazuela, Fiber-optic sensing of carbon dioxide based on excited-state proton transfer to a luminescent ruthenium(II) complex, Anal. Chem. 64, 2210-2215(1992). 

Alumina-supported Ru catalysts derived from supported ruthenium carbonyls have been reported to be effective for carbon dioxide methanation, showing higher activity than other catalysts prepared from RUCI3. The catalytic activity depended on the nuclearity of the carbonyl precursor [111]. 

An interesting application of TSIL was developed by Zhang et al for the catalytic hydrogenation of carbon dioxide to make formic acid. Ruthenium immobilized on silica was dispersed in aqueous IL solution for the reaction. H2 and CO2 were reacted to produce formic acid in high yield and selectivity. The catalyst could easily be separated from the reaction mixture by filtration and the reaction products and the IL were separated by simple distillation. The TSIL developed for this reaction system was basic with a tertiary amino group (N(CH3)2) on the cation l-(A,A-dimethylaminoethyl)-2,3-dimethylimidazolium trifluoromethanesulfonate, [mammim] [TfO]. 

Electrooxidation of carbon monoxide to carbon dioxide at platinum has been extensively studied mainly not least because of the technological importance of its role in methanol oxidation in fuel cells [5] and in poisoning hydrogen fuel cells [6]. Enhancing anodic oxidation of CO is critical, and platinum surfaces modified with ruthenium or tin, which favor oxygen atom adsorption and transfer to bound CO, can achieve this [7, 8]. 

Methane is the principal gas found with coal and oil deposits and is a major fuel and chemical used is the petrochemical industry. Slightly less than 20% of the worlds energy needs are supplied by natural gas. The United States get about 30% of its energy needs from natural gas. Methane can be synthesized industrially through several processes such as the Sabatier method, Fischer Tropsch process, and steam reforming. The Sabatier process, named for Frenchman Paul Sabatier (1854—1941), the 1912 Nobel Prize winner in chemistry from France, involves the reaction of carbon dioxide and hydrogen with a nickel or ruthenium metal catalyst C02 + 4H2 —> CH4 + 2H20. 

P2Ru(,C Hi , Ruthenium, [p-ethynediyl-bis(diphenylphosphine)]bis[unde-cacarbonyltri-, 26 277 OiiRejCa, Rhenium, octadecacarbonylbis-(p.i-carbon dioxide)tetra-, 26 111 OyNiPtiiCjiiHj, Platinate(2-), tetrakis-[tri-p-carbonyl-tricarbonyltri-... 

A powerful characteristic of the cell described above is the opportunities it affords for the determination of the compositions of both the lower (denser) and upper (lighter) phases. In particular, the combination of ATR and transmission IR spectroscopy shows the distribution of the catalyst between the two phases. For example, in the homogeneously catalyzed formylation of morpholine with carbon dioxide and hydrogen by a ruthenium catalyst, a two-phase system was found at a... 

Phenyl ethylenesulfonate, 241 Tin(IV) chloride, 300 Containing one sulfur 2,4-Bis(4-me thoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide, 38 Titanium(IV) chloride-Zinc, 310 Other five-membered heterocycles Carbon dioxide, 65 Methanesulfonyl chloride, 176 Six-membered rings Containing one nitrogen—piperidines Dichlorotris(triphenylphosphine)-ruthenium(II), 107 Mercury(II) trifluoroacetate, 175 Tetrakis(triphenylphosphine)-palladium(O), 289... 

The appropriate NMR experiment to determine whether the carbon dioxide-hydride complex is formed in equilibrium amounts in solution does not appear to have been done, but recent work on a similar system seems to support this hypothesis. Direct formation of the formate complex [(HCOO)-Ru(PPhMe2)4]+ was achieved, and when this complex is dissolved in CD2C12 at 30°C the NMR spectrum shows a broad hydride resonance centered at x = 17.4, indicating the presence of a metal-hydride complex (134), with the C02 possibly coordinated to the ruthenium. 

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