Molybdenum hydrogen reactions

The catalytic ketone hydrogenation reaction is accelerated by addition of KOH. In the presence of 25 equiv. KOH, 1 mol.% of the molybdenum complex completely hydrogenated acetophenone overnight in refluxing 2-propanol... 

A non-enzymatic color reaction for TATP and other organic peroxides was reported recently by Apblett et al. [87, 88]. The dark blue color of molybdenum hydrogen bronze suspension is changed to yellow upon oxidation with TATP. The same reagent can also be used for quick neutralization of the sensitive explosive a lasting final blue color indicates complete neutralization. The reaction with TATP is depicted in Eq. (13). 

Colorimetric field tests for TATP and HMTD were described in Section 5 dealing with peroxide-based explosives. This group contains Keinan s PEX [85] (E. Keinan, Personal Communication, February 2006) and the kit developed by Schulte-Ladbeck et al., which involves also a preliminary stage to avoid falsepositive responses by non-explosive peroxides [86]. The color change of molybdenum hydrogen bronze suspension upon reaction with TATP was recommended also as a field test. Exposure of filter paper strips which were soaked in butanol suspension of the molybdenum compound to TATP or hydrogen peroxide vapors rapidly bleaches the blue color [87, 88]. 

Sumimoto introduced a new sebacic acid process including several catalytic hydrogenation reactions.342 The synthesis starts with naphthalene, which is first partially hydrogenated to tetralin over cobalt oxide or molybdenum oxide, then to decalin over ruthenium or iridium on carbon. The selectivity to cw-decalin is better than 90%. In a later phase of the synthesis 5-cyclododecen-l-one is hydrogenated over Raney nickel to obtain a mixture of cyclododecanone and cyclodode-canol in a combined yield of 90%. The selectivity of this step is not crucial since subsequent oxidation of either compound leads to the endproduct sebacic acid. 

It is well known, even from old literature data (ref. 1) that the presence of metal promotors like molybdenum and chromium in Raney-nickel catalysts increases their activity in hydrogenation reactions. Recently Court et al (ref. 2) reported that Mo, Or and Fe-promoted Raney-nickel catalysts are more active for glucose hydrogenation than unpromoted catalysts. However the effects of metal promotors on the catalytic activity after repeated recycling of the catalyst have not been studied so far. Indeed, catalysts used in industrial operation are recycled many times, stability is then an essential criterion for their selection. From a more fundamental standpoint, the various causes of Raney-nickel deactivation have not been established. This work was intended to address two essential questions pertinent to the stability of Raney-nickel in glucose hydrogenation namely what are the respective activity losses experienced by unpromoted or by molybdenum, chromium and iron-promoted catalysts after recycling and what are the causes for their deactivation ... 

Following the development of sponge-metal nickel catalysts by alkali leaching of Ni-Al alloys by Raney, other alloy systems were considered. These include iron [4], cobalt [5], copper [6], platinum [7], ruthenium [8], and palladium [9]. Small amounts of a third metal such as chromium [10], molybdenum [11], or zinc [12] have been added to the binary alloy to promote catalyst activity. The two most common skeletal metal catalysts currently in use are nickel and copper in unpromoted or promoted forms. Skeletal copper is less active and more selective than skeletal nickel in hydrogenation reactions. It also finds use in the selective hydrolysis of nitriles [13]. This chapter is therefore mainly concerned with the preparation, properties and applications of promoted and unpromoted skeletal nickel and skeletal copper catalysts which are produced by the selective leaching of aluminum from binary or ternary alloys. 

Dybov A, Blacque O, Berke H (2011) Molybdenum nitrosyl complexes and their application in catalytic imine hydrogenation reactions. Eur J Inorg Chem 652-659... 

Continued experimentation with 3510 in 1928-29 showed that during the hydrogenation reaction molybdenum oxide changed to the sulfide, and in 1930 this led Pier to a renewed study of sulfide catalysts and to the dis-... 

COS can be converted to H2S by hydrogenation (reaction 13-2) or hydrolysis (reaction 13-6). Hydrogenation is normally accomplished with a cobalt-molybdenum cataly.st, which is also active for shift conversion. If shift conversion is not desired during the COS removal step, a hydrolysis catalyst, which is not active for shift conversion, can be utilized. One such catalyst is Topspe CKA, which consists mainly of activated alumina and is available as 3 X 10" or 6 X 10 m ()< or in.) extrudates. Table 13-16 shows operating conditions and COS converter performance for five cases. The first four are projected values for plants designed to produce synthetic natural gas (SNG), methyl alcohol (MeOH), fuel for a power plant, and ammonia. The fifth case presents actual operating data from a coal-to-ammonia plant. The COS concentrations in the product gas streams represent values close to equilibrium for the composition and temperature conditions in the converters. 

CHjiCH-CN. Volatile liquid b.p. 78"C. Manufactured by the catalytic dehydration of ethylene cyanhydrin, by the addition of hydrogen cyanide to ethyne in the presence of CuCI or the reaction of propene, ammonia and air in the presence of a molybdenum-based catalyst. 

Molybdenum hexafluoride can be prepared by the action of elemental fluorine on hydrogen-reduced molybdenum powder (100—300 mesh (ca 149—46 l-lm)) at 200°C. The reaction starts at 150°C. Owing to the heat of reaction, the temperature of the reactor rises quickly but it can be controlled by increasing the flow rate of the carrier gas, argon, or reducing the flow of fluorine. 

Depending on the ring substituent, trifluoromethoxyben2enes can be made by the sequential chlorination—fluorination of anisole(s) (351—354). A one-step process with commercial potential is the BF (or SbF2)-cataly2ed reaction of phenol with carbon tetrachloride/hydrogen fluoride (355). Aryl trifluoromethyl ethers, which may not be accessible by the above routes,may be made by fluorination of aryl fluoroformates or aryl chlorothioformates with sulfur tetrafluoride (348) or molybdenum hexafluoride (356). 

Reduction to Solid Metal. Metals having very high melting points caimot be reduced in the Hquid state. Because the separation of a soHd metallic product from a residue is usually difficult, the raw material must be purified before reduction. Tungsten and molybdenum, for instance, are prepared by reduction of a purified oxide (WO, MoO ) or a salt, eg, (NH2 2 G4, using hydrogen. A reaction such as... 

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