Olefin Epoxidation by Peroxo Complexes of Cr, Mo, and W. A Comparative Density Functional Study | Sciact - CRIS-система Института катализа

Olefin Epoxidation by Peroxo Complexes of Cr, Mo, and W. A Comparative Density Functional Study Научная публикация

Журнал

Journal of Organic Chemistry
ISSN: 0022-3263 , E-ISSN: 1520-6904

Вых. Данные

Год: 2000, Том: 65, Номер: 10, Страницы: 2996-3004 Страниц : 9 DOI: 10.1021/jo9916784

Ключевые слова

alkene; chromium derivative; ethylene; metal complex; molybdenum complex; oxygen; tungsten derivative

Авторы

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

Организации

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

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

The epoxidation of olefins by peroxo complexes of Cr(VI), Mo(VI) and W(VI) was investigated using the B3LYP hybrid density functional method. For the mono- and bisperoxo model complexes with the structures (NH3)(L)M(O)2-n(η2-O2)1+n (n = 0, 1; L = none, NH3; M = Cr, Mo, W) and ethylene as model olefin, two reaction mechanism were considered, direct oxygen transfer and a two-step insertion into the metal−peroxo bond. The calculations reveal that direct attack of the nucleophilic olefin on an electrophilic peroxo oxygen center via a transition state of spiro structure is preferred as significantly higher activation barriers were calculated for the insertion mechanism than for the direct mechanism. W complexes are the most active in the series investigated with the calculated activation barriers of direct oxygen transfer to ethylene decreasing in the order Cr > Mo > W. Barriers of bisperoxo species are lower than those of the corresponding monoperoxo species. Coordination of a second NH3 base ligand to the mono-coordinated species, (NH3)M(O)2(η2-O2) and (NH3)MO(η2-O2)2, results in a significant increase of the activation barrier which deactivates the complex. Finally, based on a molecular orbital analysis, we discuss factors that govern the activity of the metal peroxo group M(η2-O2), in particular the role of metal center.

Di Valentin C. , Gisdakis P. , Yudanov I.V. , Rösch N.
Olefin Epoxidation by Peroxo Complexes of Cr, Mo, and W. A Comparative Density Functional Study
Journal of Organic Chemistry. 2000. V.65. N10. P.2996-3004. DOI: 10.1021/jo9916784 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	26 окт. 1999 г.
Опубликована в печати:	1 мая 2000 г.

Web of science:	WOS:000087262500021
Scopus:	2-s2.0-0034685749
РИНЦ:	13358672
Chemical Abstracts:	2000:252687
Chemical Abstracts (print):	133:349915
OpenAlex:	W2085633428

БД	Цитирований
Web of science	64
Scopus	87
РИНЦ	84
OpenAlex	90