Abstract
Quantum chemical calculations of the enthalpy and activation energy of two reactions with MeO ⊙2 attacking the CH- and CH2-groups of 2,2,6,6-tetramethylpiperidineoxy-2′-butane are performed. It is shown that the cleavage of hydrogen atoms is accompanied by coordinated breaking of N-O-bonds in the former case and C-O-bonds in the latter. Based on the obtained results, a new scheme is proposed for the cyclic mechanism behind the cleavage of chains on nitroxyl radicals in oxidizing hydrocarbons and polymers that agrees with experimental data. At the center of this cyclic mechanism lies the fast exothermic reaction between peroxyl radicals and N-alkoxyamine with the cleavage of H atoms and the coordinated fragmentation of molecules. Using the model of intersecting parabolas, an algorithm for calculating the enthalpies, activation energies, and rate constants of these reactions with the participation of alkyl, alkoxy, aminyl, peroxyl, phenoxyl, thiyl, and hydroxyl radicals is proposed.
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Original Russian Text © E.T. Denisov, A.F. Shestakov, 2015, published in Zhurnal Fizicheskoi Khimii, 2015, Vol. 89, No. 8, pp. 1217–1229.
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Denisov, E.T., Shestakov, A.F. Reaction between radicals and N-alkoxyamines As coordinated cleavage with fragmentation. Russ. J. Phys. Chem. 89, 1343–1355 (2015). https://doi.org/10.1134/S0036024415080099
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DOI: https://doi.org/10.1134/S0036024415080099