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Abstract
The values of isotropic HFS constantsaN were obtained for nitroxyl radicals (NR) of the piperidine series in hexane and water. The interrelation between rate constants for NR reduction and oxidation reactions, isotropic HFS constantsaN, inductive constants σ″ of the piperidine substituents, and electrochemical characteristics of NR were found. The dependence of the rate constants for the reduction of NR by hydrazobenzene (HB) and its oxidation by tetranitromethane (TNM) upon the Hammett type inductive constantsσEPR, obtained using HFS constantsaN as the basis, was analyzed. The solvent effect on the reduction and oxidation reaction rate constants, the kinetic isotopic effect of the reduction reaction for a number of NR-HB systems, and alternative reaction mechanisms are considered.
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