Two Mechanisms of Cchlorocuprate Reactions with Alkyl Radicals: Dramatic Role of Nuclearity Научная публикация
Журнал |
Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041 |
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Вых. Данные | Год: 2014, Том: 33, Номер: 1, Страницы: 121-128 Страниц : 8 DOI: 10.1021/om400886e | ||||
Ключевые слова | Chlorine; Chlorine compounds; Copper; Copper compounds; Quantum chemistry; Reaction kinetics | ||||
Авторы |
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Организации |
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Информация о финансировании (2)
1 | Российский фонд фундаментальных исследований | 12-03-31130 |
2 | Российский фонд фундаментальных исследований | 13-03-00420 (01201353324) |
Реферат:
Interaction of copper chlorides with radicals is a key step of single electron transfer reactions and is responsible for high selectivity of copper-catalyzed radical processes. In the present article reactions of binuclear copper(II) chlorides with methyl radical were studied in the scope of density functional theory. The results of quantum-chemical calculations of potential energy surfaces allow proposing that there are at least two reasons for the lower activity of binuclear complexes Cu2Cl62– in comparison with CuCl42–. First, the radicals react with binuclear chlorocuprates via an atom transfer mechanism through an activation barrier, in contrast to the barrierless character of such reactions with partition of CuCl42–. Second, only in the systems with binuclear copper chloro complexes may an alternative path of spontaneous formation of chloroorganocuprates be realized. These intermediates may be dormant species in radical reactions.
Библиографическая ссылка:
Zubanova E.M.
, Golubeva E.N.
, Zhidomirov G.M.
Two Mechanisms of Cchlorocuprate Reactions with Alkyl Radicals: Dramatic Role of Nuclearity
Organometallics. 2014. V.33. N1. P.121-128. DOI: 10.1021/om400886e WOS Scopus РИНЦ
Two Mechanisms of Cchlorocuprate Reactions with Alkyl Radicals: Dramatic Role of Nuclearity
Organometallics. 2014. V.33. N1. P.121-128. DOI: 10.1021/om400886e WOS Scopus РИНЦ
Даты:
Поступила в редакцию: | 4 сент. 2013 г. |
Опубликована online: | 12 дек. 2013 г. |
Опубликована в печати: | 13 янв. 2014 г. |
Идентификаторы БД:
Web of science | WOS:000329879900016 |
Scopus | 2-s2.0-84892572638 |
РИНЦ | 21863162 |
Chemical Abstracts | 2013:1919416 |
Chemical Abstracts (print) | 160:100866 |
OpenAlex | W2328988755 |