Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles Научная публикация
| Журнал |
Russian Chemical Bulletin
ISSN: 1066-5285 , E-ISSN: 1573-9171 |
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| Вых. Данные | Год: 2015, Том: 64, Номер: 3, Страницы: 499-510 Страниц : DOI: 10.1007/s11172-015-0893-7 | ||||||||
| Ключевые слова | anions; donor-acceptor interactions; density functional theory; 1,2,5-chalcogenadiazoles | ||||||||
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Реферат:
Synthetic, structural, and thermodynamic aspects of the recently discovered new reaction, donor-acceptor coordination of anions (A(-)) by chalcogen atoms (E) of 1,2,5-chalcogenadiazoles, are considered. According to the quantum chemical calculations, the charge transfer from A-to the heterocycle via the mechanism of negative hyperconjugation (i.e., from the MO of the lone pair of A(-) to the virtual sigma* orbital of the E-N bond of chalcogenadiazole) depends on the nature of E and A(-), being 0.42-0.52 and 0.30-0.44 e in terms of the Mulliken and NBO methods, respectively. According to the X-ray diffraction data, the E-A(-) coordinate bond is always longer than the sum of the covalent radii but shorter than the sum of the van der Waals radii of the atoms forming the bond. The E-A(-) bond energy varies in a wide range, from similar to 25 kcal mol(-1) comparable to the energy of weak covalent bonds (e.g., internal N-N bond in organic azides) to similar to 86 kcal mol(-1) comparable to the C-C bond energy in organic compounds. The quantum chemical estimations of the thermodynamics of the donor-acceptor coordination of the anions by the chalcogen atoms of 1,2,5-chalcogenadiazoles indicate that for E = Te and Se this reaction may be of general character also covering E = S in some cases.
Библиографическая ссылка:
Semenov N.A.
, Lonchakov A.V.
, Gritsan N.P.
, Zibarev A.V.
Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles
Russian Chemical Bulletin. 2015. V.64. N3. P.499-510. DOI: 10.1007/s11172-015-0893-7 WOS Scopus РИНЦ OpenAlex
Donor-acceptor coordination of anions by chalcogen atoms of 1,2,5-chalcogenadiazoles
Russian Chemical Bulletin. 2015. V.64. N3. P.499-510. DOI: 10.1007/s11172-015-0893-7 WOS Scopus РИНЦ OpenAlex
Оригинальная:
Семенов Н.А.
, Лончаков А.В.
, Грицан Н.П.
, Зибарев А.В.
Донорно-акцепторная координация анионов атомами халькогенов 1,2,5-халькогенадиазолов
Известия Академии наук. Серия химическая.(RUSS CHEM B+). 2015. №3. С.499. РИНЦ
Донорно-акцепторная координация анионов атомами халькогенов 1,2,5-халькогенадиазолов
Известия Академии наук. Серия химическая.(RUSS CHEM B+). 2015. №3. С.499. РИНЦ
Даты:
| Опубликована в печати: | 1 мар. 2015 г. |
| Опубликована online: | 19 нояб. 2015 г. |
Идентификаторы БД:
| Web of science: | WOS:000365184100002 |
| Scopus: | 2-s2.0-84947552180 |
| РИНЦ: | 24971983 |
| OpenAlex: | W2256825265 |