Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism | Sciact - CRIS-система Института катализа

Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism Научная публикация

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

Ключевые слова

MOLECULAR-ORBITAL METHODS; AB-INITIO; OLEFIN EPOXIDATION; OXIDATION; TITANIUM; DENSITY; H2O2; DFT; REACTIVITY; TITANOSILICATES

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	Government of Catalonia	2014SGR199
3	Ministry of Economic Affairs and Digital Transformation	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.

Jimenez-Lozano P. , Skobelev I.Y. , Kholdeeva O.A. , Poblet J.M. , Carbo J.J.
Alkene Epoxidation Catalyzed by Ti-Containing Polyoxometalates: Unprecedented β‑Oxygen Transfer Mechanism
Inorganic Chemistry. 2016. V.55. N12. P.6080-6084. DOI: 10.1021/acs.inorgchem.6b00621 WOS Scopus РИНЦ CAPlusCA PMID OpenAlex

Поступила в редакцию:	11 мар. 2016 г.
Опубликована online:	27 мая 2016 г.
Опубликована в печати:	20 июн. 2016 г.

Web of science:	WOS:000378369900044
Scopus:	2-s2.0-84975482349
РИНЦ:	27138564
Chemical Abstracts:	2016:866171
Chemical Abstracts (print):	165:31133
PMID (PubMed):	27232155
OpenAlex:	W2408133551

БД	Цитирований
Web of science	39
Scopus	43
РИНЦ	34
OpenAlex	41