Quantum-Chemical Study of the Benzene Reaction with Fluorine

• Published in: Atoms Vol. 11; no. 10; p. 132
• Main Authors: Adamson, Sergey O., Kharlampidi, Daria D., Shtyrkova, Anastasia S., Umanskii, Stanislav Y., Dyakov, Yuri A., Morozov, Igor I., Golubkov, Maxim G.
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 01-10-2023
• Subjects: atomic fluorine; Benzene; Chemical properties; Chemical reactions; density functional theory; Energy; Equilibrium; Fluorine; gas-phase reaction; Hydrocarbons; Hydrogen; Mathematical analysis; Observations; Quantum chemistry; reaction mechanism; reaction path Hamiltonian; Substitution reactions; Vapor phases; Russia
• ISSN: 2218-2004; 2218-2004
• DOI: 10.3390/atoms11100132

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.