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Well-Known Mediators of Selective Oxidation with Unknown Electronic Structure: Metal-Free Generation and EPR Study of Imide-N-oxyl Radicalsстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 11 ноября 2016 г.
- Авторы: Krylov Igor B., Kompanets Mykhailo O., Novikova Katerina V., Opeida Iosip O., Kushch Olga V., Shelimov Boris N., Nikishin Gennady I., Levitsky Dmitri O., Terent'ev Alexander O.
- Журнал: The Journal of Physical Chemistry A: Molecules, Clusters, and Aerosols
- Том: 120
- Номер: 1
- Год издания: 2016
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 68
- Последняя страница: 73
- DOI: 10.1021/acs.jpca.5b10722
- Аннотация: Nitroxyl radicals are widely used in chemistry, materials sciences, and biology. Imide-N-oxyl radicals are subclass of unique nitroxyl radicals that proved to be useful catalysts and mediators of selective oxidation and CH-functionalization. An efficient metal-free method was developed for the generation of imide-N-oxyl radicals from N-hydroxyimides at room temperature by the reaction with (diacetoxyiodo)benzene. The method allows for the production of high concentrations of free radicals and provides high resolution of their EPR spectra exhibiting the superhyperfine structure from benzene ring protons distant from the radical center. An analysis of the spectra shows that, regardless of the electronic effects of the substituents in the benzene ring, the superhyperfine coupling constant of an unpaired electron with the distant protons at positions 4 and 5 of the aromatic system is substantially greater than that with the protons at positions 3 and 6 that are closer to the N-oxyl radical center. This is indicative of an unusual character of the spin density distribution of the unpaired electron in substituted phthalimide-N-oxyl radicals. Understanding of the nature of the electron density distribution in imide-N-oxyl radicals may be useful for the development of commercial mediators of oxidation based on N-hydroxyimides.
- Добавил в систему: Терентьев Александр Олегович