The Nature of Cu–C Bond and Copper Oxidation State in Chloroorganocuprates [CuClnCH3]2−n Научная публикация
Журнал |
Journal of Physical Organic Chemistry
ISSN: 0894-3230 , E-ISSN: 1099-1395 |
||||
---|---|---|---|---|---|
Вых. Данные | Год: 2013, Том: 26, Номер: 9, Страницы: 724-729 Страниц : 6 DOI: 10.1002/poc.3093 | ||||
Ключевые слова | copper, metallorganic, quantum chemistry | ||||
Авторы |
|
||||
Организации |
|
Информация о финансировании (2)
1 | Российский фонд фундаментальных исследований | 10-03-00603 |
2 | Российский фонд фундаментальных исследований | 12-03-31130 |
Реферат:
The adducts of copper(II) chloride complexes with organic radicals may be intermediates in reactions of halohydrocarbons proceeding via radical mechanism and in catalyzed by chlorocuprates. In this paper, the structure and reactivity of chloroorganocuprates with general formula [CuClnCH3]2−n (n = 0–4) were studied at density functional theory (DFT) level of theory. The comparison of geometric and electronic structures of chloroorganocuprates and corresponding copper(II) chloride complexes with the same number of chlorine atoms indicates the higher Cu oxidation state in [CuClnCH3]2−n. The Natural Bonding Orbital analysis confirms the formation of covalent σ-Cu–C bond in these complexes. The analysis of the PES of the system CuCl42−–CH3• indentifies two local minima, corresponding to CuCH3Cl42− and weak complex CuCl32−···CH3Cl, as well as transition state between them. The calculations evidence the spontaneous character of copper ion reduction with formation of halohydrocarbon by chlorine atom detachment from CuCl42− with high energetic effect.
Библиографическая ссылка:
Golubeva E.N.
, Zubanova E.M.
, Zhidomirov G.M.
The Nature of Cu–C Bond and Copper Oxidation State in Chloroorganocuprates [CuClnCH3]2−n
Journal of Physical Organic Chemistry. 2013. V.26. N9. P.724-729. DOI: 10.1002/poc.3093 WOS Scopus РИНЦ
The Nature of Cu–C Bond and Copper Oxidation State in Chloroorganocuprates [CuClnCH3]2−n
Journal of Physical Organic Chemistry. 2013. V.26. N9. P.724-729. DOI: 10.1002/poc.3093 WOS Scopus РИНЦ
Даты:
Поступила в редакцию: | 7 нояб. 2012 г. |
Принята к публикации: | 8 янв. 2013 г. |
Опубликована online: | 12 февр. 2013 г. |
Опубликована в печати: | 1 сент. 2013 г. |
Идентификаторы БД:
Web of science | WOS:000325920900007 |
Scopus | 2-s2.0-84882448653 |
РИНЦ | 20458965 |
Chemical Abstracts | 2013:245561 |
Chemical Abstracts (print) | 159:347658 |
OpenAlex | W2492009706 |