Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals


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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.

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I. Opeida

Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry

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Email: opeida_i@i.ua
乌克兰, Lviv, 79053

Yu. Litvinov

Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry

Email: opeida_i@i.ua
乌克兰, Lviv, 79053

O. Kushch

Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry

Email: opeida_i@i.ua
乌克兰, Lviv, 79053

M. Kompanets

Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry

Email: opeida_i@i.ua
乌克兰, Lviv, 79053

A. Shendrik

Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry

Email: opeida_i@i.ua
乌克兰, Kyiv, 02660

A. Matvienko

Department of Chemistry

Email: opeida_i@i.ua
乌克兰, Vinnytsia, 21021

A. Novokhatko

Department of the Physical Chemistry of Fossil Fuels, Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry

Email: opeida_i@i.ua
乌克兰, Lviv, 79053

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