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The first representative of a new family of the bridgehead-modified difluoromethylenated homofullerenes: electrochemical properties and synthetic availabilityстатья
Статья опубликована в высокорейтинговом журнале
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: 19 сентября 2015 г.
- Авторы: Rybalchenko Alexey V., Magdesieva Tatiana V., Brotsman Victor A., Belov Nikita M., Markov Vitali Yu, Ioffe Ilya N., Adrian Ruff, Paul Schuler, Bernd Speiser, Jürgen Heinze, Sidorov Lev N., Goryunkov Alexey A.
- Журнал: Electrochimica Acta
- Том: 174
- Год издания: 2015
- Издательство: Elsevier BV
- Местоположение издательства: Netherlands
- Первая страница: 143
- Последняя страница: 154
- DOI: 10.1016/j.electacta.2015.05.117
- Аннотация: The redox properties of the first member of a new family of bridgehead-modified difluoromethylenated homofullerenes, [6,6]-open C60(CF2)H2, were investigated by means of cyclic voltammetry and ESR spectroelectrochemistry. The half-life time of C60(CF2)H2–• estimated from the decay of the ESR response exceeds 25.5 min at room temperature which will be crucial for practical applications later on. The high stability of C60(CF2)H2–• was proven to be attributed to spin density delocalization over the fullerene cage as well as to the higher BDE(C–H) value for C60(CF2)H2 (as compared to C60H2). Di- and trianions of C60(CF2)H2 are less stable and undergo partial dehydrogenation. A detailed voltammetric investigation of H-transfer processes (induced by radicals, radical-anion species or by a Brønsted bases) in the anionic forms of C60(CF2)Hm (m = 0–2) was performed. It allowed suggesting a general scheme integrating various anionic forms of C60(CF2)Hmn– (n = 1–3) which was corroborated by DFT calculations as well as by a targeted synthesis of deprotonated C60(CF2)H– and C60(CF2)2– anions from C60(CF2)H2 using a Brønsted base. Based on these results, an alternative, non-electrochemical synthetic route to C60(CF2)H2 using the Zn/Cu-couple in water/toluene media was elaborated since similar processes regulate the features of hydrogenation of fullerene derivatives in both cases. Keywords: homofullerenes; C60(CF2)H2; electrochemical reduction; hydrogenation; ESR spectroscopy; DFT calculation
- Добавил в систему: Рыбальченко Алексей Владимирович