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Structure and Stability of Pentafluoroaniline and 4-Aminononafluorobiphenyl Radical Anions: Optically Detected Electron Paramagnetic Resonance, Time-Resolved Fluorescence, Time-Resolved Magnetic Field Effect, and Quantum Chemical Study Научная публикация

Журнал Journal of Physical Chemistry A
ISSN: 1089-5639
Вых. Данные Год: 2015, Том: 119, Номер: 31, Страницы: 8443-8451 Страниц : DOI: 10.1021/acs.jpca.5b02617
Авторы Borovkov Vsevolod I. 1,2 , Beregovaya Irina V. 3 , Shchegoleva Lyudmila N. 3 , Blinkova Svetlana V. 1 , Ovchinnikov Dmitry A. 1,2 , Gurskaya Larisa Yu. 4 , Shteingarts Vitaly D. 3 , Bagryansky Victor A. 1,2 , Molin Yuriy N. 1
Организации
1 (Данные Web of science) Russian Acad Sci, Siberian Branch, Voevodsky Inst Chem Kinet & Combust, Novosibirsk 630090, Russia
2 (Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3 (Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
4 (Данные Web of science) St Petersburg State Univ, Inst Chem, St Petersburg 198504, Russia

Реферат: Radical anions (RAs) are the key intermediates of the selective hydrodefluorination of polyfluoroarenes. We used the techniques of optically detected electron paramagnetic resonance (OD EPR), time-resolved fluorescence, time-resolved magnetic field effect (TR MFE), and the density functional theory to study the possibility of RAs formation from 4-aminononafluorobiphenyl (1) and pentafluoroaniline (2) and estimate their lifetimes and decay channels. To our knowledge, both RAs have not been detected earlier. We have registered the OD EPR spectrum for relatively stable in nonpolar solutions 1(-center dot) but failed to register the spectra for 2(-). However, we have managed to fix the 2(-) by the TR MFE method and obtained its hyperfine coupling constants. The lifetime of 2(-) was found to be only a few nanoseconds. The activation energy of its decay was estimated to be 3.6 +/- 0.3 kcal/mol. According to the calculation results, the short lifetime of 2(-center dot) is due to the RA fast fragmentation with the F elimination from ortho-position to the amine group. The calculated energy barrier, 3.2 kcal/mol, is close to the experimental value. The fragmentation of 2(-center dot) in a nonpolar solvent is possible due to the stabilization of the incipient F- anion by the binding with the amine group proton.
Библиографическая ссылка: Borovkov V.I. , Beregovaya I.V. , Shchegoleva L.N. , Blinkova S.V. , Ovchinnikov D.A. , Gurskaya L.Y. , Shteingarts V.D. , Bagryansky V.A. , Molin Y.N.
Structure and Stability of Pentafluoroaniline and 4-Aminononafluorobiphenyl Radical Anions: Optically Detected Electron Paramagnetic Resonance, Time-Resolved Fluorescence, Time-Resolved Magnetic Field Effect, and Quantum Chemical Study
Journal of Physical Chemistry A. 2015. V.119. N31. P.8443-8451. DOI: 10.1021/acs.jpca.5b02617 WOS Scopus OpenAlex
Даты:
Опубликована online: 23 июл. 2015 г.
Опубликована в печати: 6 авг. 2015 г.
Идентификаторы БД:
Web of science: WOS:000359331800002
Scopus: 2-s2.0-84938592777
OpenAlex: W755190172
Цитирование в БД:
БД Цитирований
Web of science 15
Scopus 15
OpenAlex 15
Альметрики: