Hydrogen Peroxide Oxygenation of Alkanes Including Methane and Ethane Catalyzed by Iron Complexes in Acetonitrile

摘要: This paper describes an investigation of the alkane oxidation with hydrogen peroxide in acetoni- trile catalyzed by iron(III) perchlorate (1), chloride (2), acetate (3) and a binuclear complex 1,4,7-triazacyclononane (4). The corresponding alkyl hydroperoxides are main products. Nevertheless kinetic study cyclo- hexane oxidation, concentrations oxygenates (cyclohexanone cyclohexanol) were measured after reduction reaction solution triphe- nylphosphine (which converts cyclohexyl hydro- to cyclohexanol). Methane ethane can be also oxidized TONs up 30 70, respectively. Chloride anions added 1 activate iron deriva- tive acetonitrile, whereas water as additive inactivates 2 H2O2 decomposition process. Pyrazine-2-carboxylic acid (PCA) reac- tion mixture decreases rate if or used catalysts, compounds 3 4 active catalysts only presence small amount PCA. kinetics selectivities oxidations demonstrated that mechanisms reactions different. Thus, 1, PCA systems oxidizing species is hydroxyl radical, catalyst has been assumed proceed (partially) formation ferryl ion, (Fe IV O) . In system (TONs attain 240) radicals generated rate-determining step monomolecular decomposi- diperoxo adduct containing one molecule. A model process which satisfactorily whole set experimental data was suggested. constants supposed equilibriums constant for decom- position estimated.