Quantum-chemical analysis of the factors affecting the stabilization of acyloxyl radicals in oxidizing systems
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It was shown on the basis of quantum-chemical analysis by the LCAO-MO SCF method in the INDO approximation that the complexation of acyloxyl radicals with copper(II) salts and also their combination with chlorine atoms are factors which lead to the stabilization of these radicals and to the possibility of the realization of reactions with retention of the carboxy1 function.
In the radical-cation RC(O)OH+ generated during the one-electron oxidation of carboxylic acids RCOOH the unpaired electron is concentrated mainly at the carbonyl oxygen atom, while in the acyloxyl radical RC(O)O it is delocalized at both oxygen atoms.
KeywordsOxidation Oxygen Copper Chlorine Carbonyl
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- 1.Yu. A. Serguchev and I. P. Beletskaya, Usp. Khim.,49, 2257 (1980).Google Scholar
- 2.R. A. Sheldon and J. K. Kochi, J. Am. Chem. Soc.,92, 493 (1970).Google Scholar
- 3.P. S. Skell and D. D. May, J. Am. Chem. Soc.,105, 3999 (1983).Google Scholar
- 4.G. L. Nikishin, I. V. Svitanko, and E. I. Troyanskii (Troyansky), J. Am. Chem. Soc., Perkin Trans.,2, 595 (1983).Google Scholar
- 5.A. I. Ioffe, É. I. Troyanskii, and G. I. Nikishin, Izv. Akad. Nauk SSSR, Ser. Khim., 1661 (1987).Google Scholar
- 6.V. E. Zubarev, É. I. Troyanskii, and G. I. Nikishin, Izv. Akad. Nauk SSSR, Ser. Khim., 2630 (1986).Google Scholar
- 7.G. M. Zhidomirov, P. V. Schastnev, and N. D. Chuvylkin, Quantum-Chemical Calculations of Magnetic-Resonance Parameters. Free Radicals [in Russian], Nauka, Novosibirsk (1978), Chap. 2.Google Scholar
- 8.N. D. Chuvylkin, Zh. Fiz. Khim.,59, 1085 (1985).Google Scholar
- 9.L. L. Miller and V. Ramachandran, J. Org. Chem.,39, 369 (1974).Google Scholar