Radical Abstraction Reactions with Concerted Fragmentation in the Chain Decay of Nitroalkanes
- Autores: Denisov E.1, Shestakov A.1
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Afiliações:
- Institute of Problems of Chemical Physics
- Edição: Volume 92, Nº 5 (2018)
- Páginas: 853-861
- Seção: Chemical Kinetics and Catalysis
- URL: https://journals.rcsi.science/0036-0244/article/view/169988
- DOI: https://doi.org/10.1134/S0036024418050072
- ID: 169988
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Resumo
Reactions of the type X• + HCR2CH2NO2 → XH + R2C=CH2 + N•O2 are exothermic, due to the breaking of weak C–N bonds and the formation of energy-intensive C=C bonds. Quantum chemistry calculations of the transition state using the reactions of Et• and EtO• with 2-nitrobutane shows that such reactions can be categorized as one-step, due to the extreme instability of the intermediate nitrobutyl radical toward decay with the formation of N•O2. Kinetic parameters that allow us to calculate the energy of activation and rate constant of such a reaction from its enthalpy are estimated using a model of intersecting parabolas. Enthalpies, energies of activation, and rate constants are calculated for a series of reactions with the participation of Et•, EtO•, RO•2, N•O2 radicals on the one hand and a series of nitroalkanes on the other. A new kinetic scheme of the chain decay of nitroalkanes with the participation of abstraction reactions with concerted fragmentation is proposed on the basis of the obtained data.
Sobre autores
E. Denisov
Institute of Problems of Chemical Physics
Autor responsável pela correspondência
Email: as@icp.ac.ru
Rússia, Chernogolovka, Moscow oblast, 142432
A. Shestakov
Institute of Problems of Chemical Physics
Email: as@icp.ac.ru
Rússia, Chernogolovka, Moscow oblast, 142432