期刊
CHEMPHYSCHEM
卷 8, 期 17, 页码 2498-2505出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.200700456
关键词
ab initio calculations; flash photolysis; photochemistry; radicals; reaction mechanisms
The kinetics of the oxidation of pyridine, 3-chloropyridine, 3-cyanopyridine, 3-methoxypyridine and 3-methylpyridine mediated by SO4 < M-> radicals are studied by flash photolysis of peroxodisulphate, S2O82-, at pH 2.5 and 9. The absolute rate constants for the reactions of both, the basic and acid forms of the pyridines, are determined and discussed in terms of the Hammett correlation. The monosubstituted pyridines react about 10 times faster with sulphate radicals than their protonated forms, the pyridine ions. The organic intermediates are identified as the corresponding hydroxypyridine radical adducts and their absorption spectra compared with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. A reaction mechanism which accounts for the observed intermediates and the pyridinols formed as products is proposed.
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