Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals
- Authors: Opeida I.A.1, Litvinov Y.E.1, Kushch O.V.1, Kompanets M.A.1, Shendrik A.N.2, Matvienko A.G.3, Novokhatko A.A.1
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Affiliations:
- Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
- Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
- Department of Chemistry
- Issue: Vol 90, No 11 (2016)
- Pages: 2142-2149
- Section: Chemical Kinetics and Catalysis
- URL: https://journals.rcsi.science/0036-0244/article/view/168921
- DOI: https://doi.org/10.1134/S0036024416110194
- ID: 168921
Cite item
Abstract
The kinetics of the reactions of hydrogen atom abstraction from the C–H bonds of substrates of different structures by phthalimide-N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor–acceptor interactions affect the reaction between phthalimide-N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.
About the authors
I. A. Opeida
Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
Author for correspondence.
Email: opeida_i@i.ua
Ukraine, Lviv, 79053
Yu. E. Litvinov
Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
Email: opeida_i@i.ua
Ukraine, Lviv, 79053
O. V. Kushch
Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
Email: opeida_i@i.ua
Ukraine, Lviv, 79053
M. A. Kompanets
Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
Email: opeida_i@i.ua
Ukraine, Lviv, 79053
A. N. Shendrik
Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
Email: opeida_i@i.ua
Ukraine, Kyiv, 02660
A. G. Matvienko
Department of Chemistry
Email: opeida_i@i.ua
Ukraine, Vinnytsia, 21021
A. A. Novokhatko
Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry
Email: opeida_i@i.ua
Ukraine, Lviv, 79053