Unexpected hydrodefluorination of 3-Cl-tetrafluoropyridine. Interpretation through analysis of the potential energy surface for its radical anion
| Autor: | R. V. Andreev, Irina V. Beregovaya, Lyudmila N. Shchegoleva |
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| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Chemistry Organic Chemistry Halide Halogenation 010402 general chemistry Photochemistry 01 natural sciences Biochemistry 0104 chemical sciences Ion Inorganic Chemistry Solvent Hydrodefluorination Fragmentation (mass spectrometry) Potential energy surface Environmental Chemistry Physical and Theoretical Chemistry Bond cleavage |
| Zdroj: | Journal of Fluorine Chemistry. 234:109513 |
| ISSN: | 0022-1139 |
| DOI: | 10.1016/j.jfluchem.2020.109513 |
| Popis: | The mechanism of the reductive dehalogenation of 3-chloro-2,4,5,6-tetrafluoropyridine has been considered in terms of quantum-chemical analysis of the potential energy surface (PES) for its daughter radical anion (RA). We analyzed PES sections along the coordinates of the RA fragmentation through the loss of a halide ion. Based on DFT calculations, a model has been built that included the solvent reorganization during the RA decomposition. The model enabled us to describe the change of the RA decay channel with an increase in solvent polarity which was found by V.P. Krasnov and V.E. Platonov, 2000. The change is due to a difference in the fine mechanisms of C-F and C-Cl bond cleavage. |
| Databáze: | OpenAIRE |
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