Unexpected hydrodefluorination of 3-Cl-tetrafluoropyridine. Interpretation through analysis of the potential energy surface for its radical anion

Unexpected hydrodefluorination of 3-Cl-tetrafluoropyridine. Interpretation through analysis of the potential energy surface for its radical anion Научная публикация

Журнал

Journal of Fluorine Chemistry
ISSN: 0022-1139

Вых. Данные

Год: 2020, Том: 234, Номер статьи : UNSP 109513, Страниц : DOI: 10.1016/j.jfluchem.2020.109513

Ключевые слова

Reductive dehalogenation; Reaction mechanism; Mixed fluoro-chloro-pyridines; Intermediate radical anions; Solvent reorganization; Potential energy surface sections

Авторы

Andreev Rodion, V ¹ , Beregovaya Irina, V ¹ , Shchegoleva Lyudmila N. ¹

Организации

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, 9 Lavrentev Ave, Novosibirsk 630090, Russia

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.

Andreev R.V. , Beregovaya I.V. , Shchegoleva L.N.
Unexpected hydrodefluorination of 3-Cl-tetrafluoropyridine. Interpretation through analysis of the potential energy surface for its radical anion
Journal of Fluorine Chemistry. 2020. V.234. UNSP 109513 . DOI: 10.1016/j.jfluchem.2020.109513 WOS Scopus РИНЦ

Опубликована в печати:

1 июн. 2020 г.

Web of science	WOS:000535980200004
Scopus	2-s2.0-85081932667
РИНЦ	43254412
OpenAlex	W3012411052