期刊
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
卷 170, 期 1-2, 页码 17-34出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/S1381-1169(01)00052-8
关键词
alcohols; alkanes; alkyl hydroperoxides; tert-butyl hydroperoxide; carboxylic acids; homogeneous catalysis; hydrogen peroxide; ketones; manganese complexes; metal-complexes; oxygenation; oxidation
The manganese(IV) complex salt [L2Mn2O3](PF6)(2) (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) (compound 1, see Scheme 1) very efficiently catalyzes the hydroperoxidation of saturated hydrocarbons, including ethane by H2O2 in acetontitrile or nitromethane solution at low (room or lower) temperature, provided a carboxylic (typically acetic) acid is present. The hydroperoxidation of tertiary positions in disubstituted cyclohexanes proceeds with partial retention of configuration in nitromethane or acetonitrile solution, while the stereoselectivity of the reaction is only negligible in acetone solution. The system H2O2-compound 1-MeCO2H also transforms secondary alcohols into the corresponding ketones with quantitative yields at room temperature within a few minutes; the yields of aldehydes and carboxylic acids in the oxidation of primary alcohols are lower. Terminal aliphatic olefins such as hexene-1 are quantitatively epoxidized by the same system in acetonitrile at room temperature within 20 min, while the epoxide yield in the analogous reaction with styrene attains only 60% under the same conditions. Finally, dimethylsulfide can be quantitatively and selectively converted into dimethylsulfoxide within 3h at room temperature. The system tert-BuOOH-compound 1 also oxidizes alkanes, addition of acetic acids has less pronounced effect on the direction and efficiency of the reaction, Two other checked derivative of Mn(IV) (compounds 2 and 3) as well a porphyrin complex of Mn(III) (compound 4) exhibited lower activity in catalysis of alkane oxidation with tert-BuOOH. (C) 2001 Elsevier Science B.V. All rights reserved.
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