Pseudorotation as a mechanism for intramolecular electron density transfer. Fragmentation of the octafluoronaphthalene radical anion

Pseudorotation as a mechanism for intramolecular electron density transfer. Fragmentation of the octafluoronaphthalene radical anion Full article

Journal

Journal of Fluorine Chemistry
ISSN: 0022-1139

Output data

Year: 2014, Volume: 163, Pages: 1-6 Pages count : DOI: 10.1016/j.jfluchem.2014.03.010

Tags

Quantum-chemical calculations; Avoided crossing; Pseudorotation; Reductive dehalogenation of polyfluoroarenes; Reaction mechanism

Authors

Beregovaya Irina V. ¹ , Shchegoleva Lyudmila N. ¹

Affiliations

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

Adiabatic potential energy surface (PES) of the octafluoronaphthalene radical anion (RA) has been investigated with the B3LYP/6-31 + G* calculations for the gas phase and polar media. In spite of the low symmetry of the RA its PES has been found to be the surface of pseudorotation. The pseudorotation is a way of intramolecular electron density transfer and so played the key role in regioselectivity of the RA fragmentation through the fluoride ion elimination. Transition states for alpha and beta C-F bond cleavage in the polar solvent were located. The noticeably lower energy barrier for the beta C-F bond cleavage explains the observed regioselectivity of the octafluoronaphthalene reductive defluorination. (C) 2014 Elsevier B.V. All rights reserved.

Beregovaya I.V. , Shchegoleva L.N.
Pseudorotation as a mechanism for intramolecular electron density transfer. Fragmentation of the octafluoronaphthalene radical anion
Journal of Fluorine Chemistry. 2014. V.163. P.1-6. DOI: 10.1016/j.jfluchem.2014.03.010 WOS Scopus РИНЦ

Published print:

Jul 1, 2014

Web of science	WOS:000337882900001
Scopus	2-s2.0-84899859242
Elibrary	21876761
OpenAlex	W2041213729