Activity of Peroxo and Hydroperoxo Complexes of Ti(IV) in Olefin Epoxidation: A Density Functional Model Study of Energetics and Mechanism | Sciact - CRIS-система Института катализа

Activity of Peroxo and Hydroperoxo Complexes of Ti(IV) in Olefin Epoxidation: A Density Functional Model Study of Energetics and Mechanism Научная публикация

Журнал

European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682

Вых. Данные

Год: 1999, Номер: 12, Страницы: 2135-2145 Страниц : 11 DOI: 10.1002/(SICI)1099-0682(199912)1999:12<2135::AID-EJIC2135>3.0.CO;2-X

Ключевые слова

Density functional calculations, Epoxidation, Peroxo complexes, Titanium, Transition states

Авторы

Yudanov Ilya V. ^1,2 , Gisdakis Philip ¹ , Di Valentin Cristiana ^1,3 , Rösch Notker ¹

Организации

1	Institut für Physikalische und Theoretische Chemie, Technische Universität München, D-85747 Garching, Germany
2	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, 630090 Novosibirsk, Russia
3	Dipartimento di Chimica Organica, Universita` degli Studi di Pavia, V. le Taramelli 10, I-27100 Pavia, Italy

Информация о финансировании (4)

1	Federal Ministry of Science, Research and Economics	03D0050B
2	International Association for the Promotion of Co-operation with Scientists from the New Independent States of the Former Soviet Union	IR-97-1071
3	Verband der Chemischen Industrie
4	German Research Foundation

Epoxidation of olefins by TiIV peroxo and hydroperoxo (alkylperoxo) complexes was investigated using a hybrid DFT method (B3LYP). Reaction energies and activation barriers for direct oxygen transfer to ethylene as a model olefin were computed for various model complexes to compare the epoxidation activity of Ti(η2-O2) and TiOOR (R = H, CH3) moieties. The activity of complexes with a Ti(O2) peroxo group is shown to be essentially quenched when the coordination sphere of the complex is saturated by strongly basic (σ-donor) ligands. In contrast, the activity of a TiOOH functional group depends only weakly on the saturation of the coordination sphere of the Ti center. Substitution of methyl for hydrogen in a TiOOH group is found to slightly increase the activation barrier of epoxidation. The computational results give preference to reaction paths that involve TiOOR species. The factors governing the activity of Ti(O2) and TiOOR groups, in particular the effects of donor ligands, are discussed on the basis of a molecular orbital analysis.

Yudanov I.V. , Gisdakis P. , Di Valentin C. , Rösch N.
Activity of Peroxo and Hydroperoxo Complexes of Ti(IV) in Olefin Epoxidation: A Density Functional Model Study of Energetics and Mechanism
European Journal of Inorganic Chemistry. 1999. N12. P.2135-2145. DOI: 10.1002/(SICI)1099-0682(199912)1999:12<2135::AID-EJIC2135>3.0.CO;2-X WOS Scopus РИНЦ CAPlusCA OpenAlex OpenAlex

Поступила в редакцию:	18 июн. 1999 г.
Опубликована online:	15 нояб. 1999 г.
Опубликована в печати:	1 дек. 1999 г.

Web of science:	WOS:000083941600005
Scopus:	2-s2.0-0032700147
РИНЦ:	13320522
Chemical Abstracts:	1999:761698
Chemical Abstracts (print):	132:92928
OpenAlex:	W2083073083 \| W4241480951

БД	Цитирований
Web of science	72
Scopus	77
РИНЦ	82
OpenAlex	60 1