Nitrogen monoxide reductive chemistry

The first is biomedicine. The discovery of superoxide dismutase and nitrogen monoxide as messengers has led to an explosive growth in articles in which one-electron oxidations and reductions have been explored. Organic radicals play an important role in the treatment of cancers. The other is atmospheric chemistry where the modeling of reactions requires accurate reduction potentials (Stanbury 1989, Wardman 1989). 

Ishihara T,Kagawa M, Mizuhara Y et al (1992) Selective reduction of nitrogen monoxide with propene over Cu-silicoaluminophosphate (SAPO) under oxidizing atmosphere. Chemistry Letters 2119-2122. 

The redox chemistry of nitrogen monoxide has attracted further attention partly in an environmental context. It is reduced by Fe(II) to give HNO and hence N2O. Further reduction to N2 does not occur below pH The first stage is the formation of the Fe(II) nitrosyl complex,... 

In addition to the successful reductive carbonylation systems utilizing the rhodium or palladium catalysts described above, a nonnoble metal system has been developed (27). When methyl acetate or dimethyl ether was treated with carbon monoxide and hydrogen in the presence of an iodide compound, a trivalent phosphorous or nitrogen promoter, and a nickel-molybdenum or nickel-tungsten catalyst, EDA was formed. The catalytst is generated in the reaction mixture by addition of appropriate metallic complexes, such as 5 1 combination of bis(triphenylphosphine)-nickel dicarbonyl to molybdenum carbonyl. These same catalyst systems have proven effective as a rhodium replacement in methyl acetate carbonylations (28). Though the rates of EDA formation are slower than with the noble metals, the major advantage is the relative inexpense of catalytic materials. Chemistry virtually identical to noble-metal catalysis probably occurs since reaction profiles are very similar by products include acetic anhydride, acetaldehyde, and methane, with ethanol in trace quantities. 

Reasons for interest in the catalyzed reactions of NO, CO, and COz are many and varied. Nitric oxide, for example, is an odd electron, hetero-nuclear diatomic which is the parent member of the environmentally hazardous oxides of nitrogen. Its decomposition and reduction reactions, which occur only in the presence of catalysts, provide a stimulus to research in nitrosyl chemistry. From a different perspective, the catalyzed reactions of CO and COz have attracted attention because of the need to develop hydrocarbon sources that are alternatives to petroleum. Carbon dioxide is one of the most abundant sources of carbon available, but its utilization will require a cheap and plentiful source of hydrogen for reduction, and the development of catalysts that will permit reduction to take place under mild conditions. The use of carbon monoxide in the development of alternative hydrocarbon sources is better defined at this time, being directly linked to coal utilization. The conversion of coal to substitute natural gas (SNG), hydrocarbons, and organic chemicals is based on the hydrogen reduction of CO via methanation and the Fischer-Tropsch synthesis. Notable successes using heterogeneous catalysts have been achieved in this area, but most mechanistic proposals remain unproven, and overall efficiencies can still be improved. 

Unlike cobalt and rhodium, the chemistry of polynuclear iridium carbonyl derivatives has not been studied in detail (15a). Reduction of Ir4(CO)i2 under carbon monoxide with K2C03 in methanol gives the yellow tetranuclear hydride derivative [Ir4(CO)nH], whereas under nitrogen the brown dianion [Ir8(CO)2o]2- has been isolated as a tetraalkylam-monium salt (97). It has been suggested that the structure of the dianion could result from the linking of two iridium tetrahedra, although its formulation so far is based only on elemental analyses. Clearly such an interesting compound deserves further chemical and structural characterization. 

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