Hydrogenation chromium-catalyzed

Erankel, E. (1970) Conversion of polyunsaturates in vegetable oils to cis Monounsaturates by homogeneous hydrogenation catalyzed with chromium carbonyls./.Am. Oil Chem. Soc., 47, 11-14. 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

Another subject of dispute was the mechanism of the photochemical, chromium carbonyl catalyzed hydrogenation of dienes /42/. The question here was whether the catalytic reaction is started by the dissociation of CO (Equation 42) or by the dissociation of the coordinated diene (Equation 43) /42, 43/. 

Chromox [Chromium oxidation] A process for destroying organic pollutants in aqueous wastes by oxidation with hydrogen peroxide, catalyzed by Cr6+. Developed by British Nuclear Fuels in 1995, originally for use in nuclear reprocessing. 

Eastman-Halcon A process for making acetic anhydride from syngas. The basic process is the carbonylation of methyl acetate. Methanol is made directly from the carbon monoxide and hydrogen of syngas. Acetic acid is a byproduct of the cellulose acetate manufacture for which the acetic anhydride is needed. The carbonylation is catalyzed by rhodium chloride and chromium hexacarbonyl. 

Salzer et al. prepared a set of planar-chiral diphosphine ligands based on the arene chromium tricarbonyl backbone (Fig. 36.3) [21]. The straightforward four-step synthetic route allowed the preparation of 20 ligands of this family. These ligands were tested in Ru- and Rh-catalyzed enantioselective hydrogenation of various substrates, including the standard C=C substrates (dimethyl itaconate, methyl-2-acetamidocinnamate, methyl-2-acetamidoacrylate) as well as MEA-imine (l-(methoxymethyl)ethylidene-methylethylaniline) and ethyl pyruvate. Moderate conversions and ee-values were obtained. 

Nickel catalysts, 77 94, 99, 109 precipitated, 77 121-122 Nickel-catalyzed dinitrotoluene hydrogenation, 25 194 Nickel chelates, 77 117 Nickel chloride hexahydrate, 77 109, 110 Nickel chromate, molecular formula, properties, and uses, 6 562t Nickel-chromium alloy 600, in galvanic series, 7 805t... 

Hydrogen transfer reactions from an alcohol to a ketone (typically acetone) to produce a carbonyl compound (the so-caUed Oppenauer-type oxidation ) can be performed under mild and low-toxicity conditions, and with high selectivity when compared to conventional methods for oxidation using chromium and manganese reagents. While the traditional Oppenauer oxidation using aluminum alkoxide is accompanied by various side reactions, several transition-metal-catalyzed Oppenauer-type oxidations have been reported recently [27-29]. However, most of these are limited to the oxidation of secondary alcohols to ketones. 

Although all of the above elements catalyze hydrogenation, only platinum, palladium, rhodium, ruthenium and nickel are currently used. In addition some other elements and compounds were found useful for catalytic hydrogenation copper (to a very limited extent), oxides of copper and zinc combined with chromium oxide, rhenium heptoxide, heptasulfide and heptaselen-ide, and sulfides of cobalt, molybdenum and tungsten. 

With the same excess of catalysts hydrogenations of the esters over Raney nickel could be carried out at temperatures as low as 25-125° at 350atm with comparable results (80% yields). However, benzene rings were saturated under these conditions [55]. In addition to nickel and copper, zinc and chromium oxides, rhenium obtained by reduction of rhenium heptoxide also catalyzes hydrogenation of esters to alcohols at 150-250° and 167-340 atm in 35-100% yields [42]. 

The impure metal dissolves easily in mineral acids and in fluoroboric, sulfamic am trifluoromethylsulfonic acids to give Cr2+ solutions, but oxidation of Cr2+ by hydrogen ion (equation 6), °(Cr3+, Cr2+) = —0.41 V) even in an inert atmosphere is catalyzed by thi impurities and various ions.71 Indefinitely stable chromium(II) solutions can be obtained fron the pure (electrolytic) metal (99.5% or better), although the reaction with acid may need to b< initiated by heat and the inclusion of some metal previously attacked by acid. The use of ai excess of metal, which can be filtered off, ensures that little acid remains. In near neutra solution the hydrogen potential is lowered and the Cr2+ ion is stable. In alkaline condition brown Cr(OH)2, which slowly reduces water, precipitates.73,73... 

Fluorinated chromia used to catalyze the isomerization reaction of CHF2CHF2 to CF3CH2F, also exhibited evidence for the importance of chromium in higher oxidation states. FTIR spectroscopic measurements of CO adsorption confirmed the occurrence of Cr4+ and Cr5+ on the surface of chromia catalysts before being used [52]. During the activation, Cr4+ and Cr5+ sites were reduced and enhanced activity of the catalyst was observed. The reaction pathway proposed for isomerization involves the formation of hydrogen fluoride due to the degradation reaction of the fluoroalkane. 

---