Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Inorganic Chemistry
ISSN: 0020-1669
, E-ISSN: 1520-510X
|
| Вых. Данные |
Год: 2016,
Том: 55,
Номер: 12,
Страницы: 6080-6084
Страниц
: 5
DOI:
10.1021/acs.inorgchem.6b00621
|
| Авторы |
Jimenez-Lozano Pablo
1
,
Skobelev Igor Y.
2,3
,
Kholdeeva Oxana A.
2,3
,
Poblet Josep M.
1
,
Carbo Jorge J.
1
|
| Организации |
| 1 |
Department de Química Física i Inorganica, Universitat Rovira i Vigili, Marcel ̀ ·lí Domingo s/n, 43007 Tarragona, Spain
|
| 2 |
Boreskov Institute of Catalysis, Prospekt Akademika Lavrentiev 5, Novosibirsk 630090, Russia
|
| 3 |
Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
|
|
Информация о финансировании (3)
|
1
|
Федеральное агентство научных организаций России
|
V.44.2.2.
|
|
2
|
Generalitat de Catalonia
|
2014SGR199
|
|
3
|
Ministerio de Economía y Empresa
|
CTQ2014-52774-P
|
A DFT study revealed that the mechanism of alkene epoxidation with hydrogen peroxide catalyzed by Ti-containing polyoxometalates (POMs) depends on the Ti coordination environment: For rigid and hindered Ti centers, the unprecedented β-oxygen transfer from the titanium hydroperoxo species becomes favored over the α-oxygen one. Improving the model for catalyst description, the calculations were able to reproduce the Arrhenius activation energy values determined in kinetic studies. Unlike protonation, the possible ion-pairing between POMs and countercations has a minor effect on the electrophlicity of the catalyst and, consequently, on the activity of epoxidation.