Abstract
Quantum chemical calculations of the dissociation energy of the C-H bond in the α-hydroperoxide fragment of Me2CHOOH were carried out. It was shown that abstraction of H atom is accompanied by dissociation of the O-O bond. Density functional calculations of transition states of the reactions of ·CH3, CH3OO·, and HO2 · radicals with the C-H bond in the α-hydroperoxide fragment of Me2CHOOH were carried out. It was established that H atom abstraction is accompanied by concerted dissociation of the O-O bond. For 45 peroxides R1R2CHOOH, R1R2CHOOR3, and R1R2CHOOC(O)R3 (R1, R2 = H, Me, Et, Ph, H2C=CH), the enthalpies of H atom abstraction from the C-H bond in the a-hydroperoxide fragment with fragmentation of the peroxides at the O-O bond were calculated. The kinetic parameters for 12 classes of radical abstraction reactions with fragmentation of molecules were calculated from experimental data within the framework of the model of intersecting parabolas. The activation energies and reaction rate constants of H atom abstraction from C-H bonds of a-peroxide fragments involving peroxyl and alkyl radicals were determined for 45 peroxides of different structure.
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Dedicated to Academician of the Russian Academy of Sciences O. M. Nefedov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 17–27, January, 2012.
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Denisov, E.T., Shestakov, A.F. Free radical abstraction of H atom from peroxides with concerted dissociation of O-O bond. Russ Chem Bull 61, 17–27 (2012). https://doi.org/10.1007/s11172-012-0003-z
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DOI: https://doi.org/10.1007/s11172-012-0003-z