Solvent-Free Allylic Oxidation of Alkenes with O2 Mediated by Fe- and Cr-MIL-101 | Sciact - CRIS-система Института катализа

Solvent-Free Allylic Oxidation of Alkenes with O2 Mediated by Fe- and Cr-MIL-101 Научная публикация

Журнал

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Вых. Данные

Год: 2013, Том: 298, Страницы: 61-69 Страниц : 9 DOI: 10.1016/j.jcat.2012.11.003

Ключевые слова

Alkenes, Allylic oxidation, Heterogeneous catalysis, Metal-organic framework, MIL-101, Molecular oxygen

Авторы

Skobelev Igor Y. ^1,2 , Sorokin Alexander B. ² , Kovalenko Konstantin A. ³ , Fedin Vladimir P. ³ , Kholdeeva Oxana A. ¹

Организации

1	Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk 630090, Russia
2	IRCELYON, CNRS, 2, Avenue A. Einstein, 69626 Villeurbanne Cedex, France
3	Nikolaev Institute of Inorganic Chemistry, pr. Lavrentieva 3, Novosibirsk 630090, Russia

Информация о финансировании (4)

1	Российский фонд фундаментальных исследований	09-03-93109
2	Министерство образования и науки Российской Федерации	02.740.11.0628
3	Министерство образования и науки Российской Федерации	1729.2012.3
4	Посольство Франции в России

Catalytic properties of Fe-MIL-101 and Cr-MIL-101 metal–organic frameworks in the solvent-free oxidation of cyclohexene and α-pinene with molecular oxygen have been explored. Both catalysts allow alkene oxidation under mild conditions (1 bar O2, 40–60 °C) and afford allylic oxidation products. The nature of catalysis and the product distribution strongly depend on the nature of the transition metal. Cr-MIL-101 behaves as truly heterogeneous catalyst to give predominantly α,β-unsaturated ketones. Catalysis over Fe-MIL-101 has true heterogeneous nature only at 40 °C, producing mainly 2-cyclohexene-1-ol. At 50–60 °C, iron leaching into solution occurs, leading to cyclohexenyl hydroperoxide as the major product. Under optimal conditions, both catalysts can be reused several times without suffering a loss of the catalytic properties. Rate-retarding and rate-accelerating effects of inhibitors and initiators, respectively, indicate radical chain mechanism. Different pathways for transformation of hydroperoxide have been suggested to rationalize the observed differences in the reaction selectivities over Cr- and Fe-MIL-101.

Skobelev I.Y. , Sorokin A.B. , Kovalenko K.A. , Fedin V.P. , Kholdeeva O.A.
Solvent-Free Allylic Oxidation of Alkenes with O2 Mediated by Fe- and Cr-MIL-101
Journal of Catalysis. 2013. V.298. P.61-69. DOI: 10.1016/j.jcat.2012.11.003 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	20 июл. 2012 г.
Принята к публикации:	3 нояб. 2012 г.
Опубликована online:	22 дек. 2012 г.
Опубликована в печати:	1 февр. 2013 г.

Web of science:	WOS:000316155700007
Scopus:	2-s2.0-84873398320
РИНЦ:	20428582
Chemical Abstracts:	2013:192121
Chemical Abstracts (print):	158:334082
OpenAlex:	W2030489223

БД	Цитирований
Web of science	206
Scopus	218
РИНЦ	206
OpenAlex	223