Reaction of atomic fluorine with benzene

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Abstract

Benzene is one of the most common classes of chemicals in industry. As a rule, it enters the atmosphere as a result of man-made accidents, during the evaporation of solvents, etc. Benzene and its derivatives are toxic and have a negative impact on the environment and the human body. Therefore, issues of benzene transformation in the atmosphere are of increased interest. In present work, the structures and electronic energies of equilibrium configurations and transition complexes of the C₆H₆ F and C₆H₆F⁺ systems are calculated using the density functional theory. It has been shown that the interaction of benzene with atomic fluorine can proceed through two channels, i.e. the elimination of hydrogen with the formation of a phenyl radical and the addition of a fluorine atom with the formation of an ipso-fluorocyclohexadienyl radical. It has been established that for the dissociation of ipso-fluorocyclohexadienyl radical into fluorobenzene and atomic hydrogen, it is necessary to expend about 27 kcal/mol. This indicates a low probability of this process occurring at low temperatures. Under experimental conditions, when the temperature of fluorine atoms is about 1000 K, the ipso-fluorocyclohexadienyl radical decomposes to form fluorobenzene. In this case, the occurrence of secondary reactions is unlikely. The conclusions drawn from the analysis of the results of quantum chemical calculations are in good agreement with the experimental data.

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About the authors

S. O. Adamson

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Author for correspondence.
Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow

D. D. Kharlampidi

Moscow State Pedagogical University; RUDN University

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow; Moscow

A. S. Shtyrkova

Moscow State Pedagogical University

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow

S. Y. Umanskii

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow

Y. A. Dyakov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences; Research Center for Environmental Changes, Academia Sinica

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow; Taipei, Republic of China

I. I. Morozov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow

I. G. Stepanov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow

M. G. Golubkov

Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences

Email: sergey.o.adamson@gmail.com
Russian Federation, Moscow

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2. Fig. 1. Structural models of ipso- (a), ortho- (b), meta- (c), para- (d) fluorocyclohexadienyl radicals, the C₆H₅F · H complex (d) and the transition complexes TS₁ (e) and TS₂ (g). Internuclear distances are given in angstroms, angles in degrees.

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3. Fig. 2. Structural models of cations of ipso- (a), ortho- (b), F-isomer (c) of fluorocyclohexadienyl radicals and transition complexes TSoi (g), TSoF (e) and TSiF (e). The indices in the designations of the transition complexes correspond to the nomenclature of isomers: o – ortho-, i – ipso-, F-isomers. Internuclear distances are given in angstroms, angles – in degrees.

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4. Fig. 3. Reactions of hydrogen abstraction and substitution in benzene. Relative energies are given in kcal/mol.

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5. Fig. 4. Isomerization and decomposition reactions of the C₆H₆ F⁺ cation. Relative energies are given in kcal/mol.

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6. Fig. 5. Absorption lines of the C₆H₆ F radical in the IR region of the spectrum: red dark lines are experimental data [10], white rectangles are scaled values ​​of the calculated frequencies of fundamental vibrations (scaling factor – 0.98).

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