Free-Radical Abstraction Reactions with Concerted
Fragmentation and NO Formation

E. T. Denisov*, A. F. Shestakov, and N. S. Emel’yanova

Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia

*e-mail: det@icp.ac.ru

Received September 25, 2015

Abstract—The enthalpy and activation energy of reactions involving attack by and on CH₂ groups
of 2-butyl nitrite and 2-nitrosobutane have been calculated by quantum chemical methods. The abstraction of a
hydrogen atom is accompanied, in the former case, by concerted N–O bond breaking and, in the latter case, by
concerted C–N bond breaking, resulting in NO^• formation. On the basis of the results obtained, an algorithm
has been developed within the intersecting parabolas model for calculating the enthalpies, activation energies,
and rate constants of these types of reactions involving alkyl, alkoxyl, aminyl, peroxyl, phenoxyl, thiyl, and
hydroxyl radicals.

Keywords: alkyl nitrite, nitrosoalkane, density functional method, intersecting parabolas model, abstraction
with fragmentation, free radicals

DOI: 10.1134/S0023158416030046

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