Quantum-Chemical Study of the Benzene Reaction with Fluorine

The reaction of benzene with fluorine atoms may be of interest as a source of phenyl and ipso-fluorocyclohexadienyl radicals or as a method for fluorobenzene gas phase synthesis. The structures and electronic energies of the equilibrium configurations and transition complexes of the C6H6F system are calculated in the density functional approximation. It was found that the interaction of benzene with atomic fluorine can proceed via two channels: hydrogen abstraction with the phenyl radical formation, and hydrogen substitution with the ipso-fluorocyclohexadienyl radical as primary product. Then the dissociation of the ipso-fluorocyclohexadienyl radical leads to creation of fluorobenzene and atomic hydrogen. The initiation of this reaction requires the activation energy near 27 kcal/mol, which indicates the low probability of this process, occurring at temperatures close to the standard (298 K). The calculations of the fluorocyclohexadienyl isomers and their cations also indicate that the formation of fluorobenzene as a product of secondary reactions is unlikely. The conclusions are confirmed by experimental data. © 2023 by the authors.

Авторы
Adamson S.O. , Kharlampidi D.D. , Shtyrkova A.S. , Umanskii S.Y. , Dyakov Y.A. , Morozov I.I. , Golubkov M.G.
Журнал
Издательство
Multidisciplinary Digital Publishing Institute (MDPI)
Номер выпуска
10
Язык
Английский
Статус
Опубликовано
Номер
132
Том
11
Год
2023
Организации
  • 1 Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow, 119334, Russian Federation
  • 2 Department of Biology and Chemistry, Moscow State Pedagogical University, Moscow, 119435, Russian Federation
  • 3 Department of Gravitation and Cosmology, RUDN University, Moscow, 117198, Russian Federation
  • 4 Research Center for Environmental Changes, Academia Sinica, Taipei, 115, Taiwan
Ключевые слова
atomic fluorine; benzene; density functional theory; gas-phase reaction; reaction mechanism; reaction path Hamiltonian
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