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 <i>ipso</i>-fluorocyclohexadienyl radicals or as a method for fluorobenzene gas phase synthesis. The structures and electronic energies of the equilibrium configurations and transition complexes of t...
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2023-10-01
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| author | Sergey O. Adamson Daria D. Kharlampidi Anastasia S. Shtyrkova Stanislav Y. Umanskii Yuri A. Dyakov Igor I. Morozov Maxim G. Golubkov |
| author_facet | Sergey O. Adamson Daria D. Kharlampidi Anastasia S. Shtyrkova Stanislav Y. Umanskii Yuri A. Dyakov Igor I. Morozov Maxim G. Golubkov |
| author_sort | Sergey O. Adamson |
| collection | DOAJ |
| description | The reaction of benzene with fluorine atoms may be of interest as a source of phenyl and <i>ipso</i>-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 C<sub>6</sub>H<sub>6</sub>F 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 <i>ipso</i>-fluorocyclohexadienyl radical as primary product. Then the dissociation of the <i>ipso</i>-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. |
| first_indexed | 2024-03-10T21:27:53Z |
| format | Article |
| id | doaj.art-eb111262d18f434b8893b3b1bea3b3a7 |
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| issn | 2218-2004 |
| language | English |
| last_indexed | 2024-03-10T21:27:53Z |
| publishDate | 2023-10-01 |
| publisher | MDPI AG |
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| spelling | doaj.art-eb111262d18f434b8893b3b1bea3b3a72023-11-19T15:37:22ZengMDPI AGAtoms2218-20042023-10-01111013210.3390/atoms11100132Quantum-Chemical Study of the Benzene Reaction with FluorineSergey O. Adamson0Daria D. Kharlampidi1Anastasia S. Shtyrkova2Stanislav Y. Umanskii3Yuri A. Dyakov4Igor I. Morozov5Maxim G. Golubkov6Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 119334 Moscow, RussiaDepartment of Biology and Chemistry, Moscow State Pedagogical University, 119435 Moscow, RussiaDepartment of Biology and Chemistry, Moscow State Pedagogical University, 119435 Moscow, RussiaSemenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 119334 Moscow, RussiaSemenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 119334 Moscow, RussiaSemenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 119334 Moscow, RussiaSemenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 119334 Moscow, RussiaThe reaction of benzene with fluorine atoms may be of interest as a source of phenyl and <i>ipso</i>-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 C<sub>6</sub>H<sub>6</sub>F 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 <i>ipso</i>-fluorocyclohexadienyl radical as primary product. Then the dissociation of the <i>ipso</i>-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.https://www.mdpi.com/2218-2004/11/10/132gas-phase reactionreaction mechanismreaction path Hamiltonianbenzeneatomic fluorinedensity functional theory |
| spellingShingle | Sergey O. Adamson Daria D. Kharlampidi Anastasia S. Shtyrkova Stanislav Y. Umanskii Yuri A. Dyakov Igor I. Morozov Maxim G. Golubkov Quantum-Chemical Study of the Benzene Reaction with Fluorine Atoms gas-phase reaction reaction mechanism reaction path Hamiltonian benzene atomic fluorine density functional theory |
| title | Quantum-Chemical Study of the Benzene Reaction with Fluorine |
| title_full | Quantum-Chemical Study of the Benzene Reaction with Fluorine |
| title_fullStr | Quantum-Chemical Study of the Benzene Reaction with Fluorine |
| title_full_unstemmed | Quantum-Chemical Study of the Benzene Reaction with Fluorine |
| title_short | Quantum-Chemical Study of the Benzene Reaction with Fluorine |
| title_sort | quantum chemical study of the benzene reaction with fluorine |
| topic | gas-phase reaction reaction mechanism reaction path Hamiltonian benzene atomic fluorine density functional theory |
| url | https://www.mdpi.com/2218-2004/11/10/132 |
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