Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies Научная публикация
| Журнал |
European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682 |
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| Вых. Данные | Год: 2010, Том: 2010, Номер: 33, Страницы: 5312-5317 Страниц : 6 DOI: 10.1002/ejic.201000615 | ||||||
| Ключевые слова | Density functional calculations, Epoxidation, Hydrogen peroxide, Polyoxometalates, Titanium | ||||||
| Авторы |
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| Организации |
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Информация о финансировании (5)
| 1 | Российский фонд фундаментальных исследований | 09-03-91333 |
| 2 | Ministry of Economic Affairs and Digital Transformation | CTQ2008-06549-C02-01/BQU |
| 3 | Ministry of Economic Affairs and Digital Transformation | |
| 4 | Government of Catalonia | 2009SGR462 |
| 5 | Government of Catalonia | XRQTC |
Реферат:
Epoxidation of a range of alkenes with aqueous H2O2 easily proceeds in the presence of the dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8– (1), which contains five-coordinate Ti atoms. The results of product and kinetics studies support a mechanism that involves a reversible interaction between H2O2 and the Ti–OH group of 1 to produce a titanium hydroperoxo complex followed by electrophilic oxygen atom transfer from the hydroperoxo ligand to the alkene substrate in the rate-limiting step. The effect of the alkene substrate nature has been investigated at the DFT level. A clear correlation between the energy of πC=C orbitals in the alkene and the turnover frequency values has been found, thereby indicating that the higher nucleophilicity of the alkene, the higher the reactivity. ONIOM (ONIOM = our own n-layered integrated molecular orbital and molecular mechanics) calculations have been employed to evaluate the role of steric effects of alkene substituents. The calculations show that the steric bulk can play a secondary role and tunes the activity in specific cases such as trans-stilbene.
Библиографическая ссылка:
Donoeva B.G.
, Trubitsina T.A.
, Antonova N.S.
, Carbo J.J.
, Poblet J.M.
, Al-Kadamany G.
, Kortz U.
, Kholdeeva O.A.
Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies
European Journal of Inorganic Chemistry. 2010. V.2010. N33. P.5312-5317. DOI: 10.1002/ejic.201000615 WOS Scopus РИНЦ CAPlusCA OpenAlex
Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies
European Journal of Inorganic Chemistry. 2010. V.2010. N33. P.5312-5317. DOI: 10.1002/ejic.201000615 WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
| Поступила в редакцию: | 2 июн. 2010 г. |
| Опубликована online: | 15 окт. 2010 г. |
| Опубликована в печати: | 1 нояб. 2010 г. |
Идентификаторы БД:
| Web of science: | WOS:000285229800015 |
| Scopus: | 2-s2.0-78649237658 |
| РИНЦ: | 16694044 |
| Chemical Abstracts: | 2010:1415615 |
| Chemical Abstracts (print): | 154:109014 |
| OpenAlex: | W2008112490 |