Determination of the Rate Constant of the Reaction of Benzene with Atomic Fluorine by the Method of Competing Reactions

Vasiliev, E. S.; Volkov, N. D.; Karpov, G. V.; Morozov, I. I.; Nigmatullin, D. R.; Saigina, E. A.; Savilov, S. V.; Umanskii, S. Ya.; Butkovskaya, N. I.

doi:10.1134/s1990793121050213

Cited by 6 publications

(2 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This estimate, despite its approximate nature, confirms the possibility of the formation of fluorobenzene in the reaction (6). Note, that the dissociation of F 2 under the influence of a microwave discharge is a typical method for fluorine atomization in the method of competing reactions [30,39,45]. In this case, the degree of F 2 dissociation was estimated at approximately 97%, which indicates a higher temperature of the reaction mixture compared to previous results [12,13].…”

Section: Resultssupporting

confidence: 73%

“…As mentioned above, the stage of dissociation of ipso-fluorocyclohexadienyl radical has a rather high threshold (near 26.9 kcal/mol), which indicates about low probability of this reaction occurring under standard conditions. However, in most studies, the source of fluorine atoms was the dissociation reaction F 2 → 2F, activated thermally [4][5][6][7][8][9]12,13] or by high-frequency discharge [2,30,39]. The oven temperature ranged from 1023 K [4][5][6][7][8][9] up to 1100 K [12,13] whereas the fluorine thermal atomization threshold is about 650 K [12].…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Quantum-Chemical Study of the Benzene Reaction with Fluorine

Adamson,

Kharlampidi,

Shtyrkova

et al. 2023

Atoms

View full text Add to dashboard Cite

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.

show abstract