Remarkably Fast Oxidation of Alkanes by Hydrogen Peroxide Catalyzed by a Tetracopper(II) Triethanolaminate Complex: Promoting Effects of Acid Co-Catalysts and Water, Kinetic and Mechanistic Features | Sciact - CRIS-система Института катализа

Remarkably Fast Oxidation of Alkanes by Hydrogen Peroxide Catalyzed by a Tetracopper(II) Triethanolaminate Complex: Promoting Effects of Acid Co-Catalysts and Water, Kinetic and Mechanistic Features Научная публикация

Журнал

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

Вых. Данные

Год: 2009, Том: 268, Номер: 1, Страницы: 26-38 Страниц : 13 DOI: 10.1016/j.jcat.2009.08.016

Ключевые слова

Acid promoters, Alkanes oxidation, Copper complexes, Cyclohexane, Homogeneous catalysis, Hydrogen peroxide, Water

Авторы

Kirillova Marina V. ¹ , Kozlov Yuriy N. ² , Shulʹpina Lidia S. ³ , Lyakin Oleg Y. ⁴ , Kirillov Alexander M. ¹ , Talzi Evgenii P. ⁴ , Pombeiro Armando J.L. ¹ , Shulʹpin Georgiy B. ²

Организации

1	Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
2	Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia
3	Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ulitsa Vavilova, dom 28, Moscow 119991, Russia
4	Boreskov Institute of Catalysis, Russian Academy of Sciences, Prospekt Akad. Lavrentieva, dom 5, Novosibirsk 630090, Russia

Информация о финансировании (2)

1	Российский фонд фундаментальных исследований	06-03-32344
2	European Commission

The kinetic and mechanistic features of alkane oxidations to the corresponding alkyl hydroperoxides (main primary products), alcohols and ketones (secondary products) in the systems composed of tetracopper(II) triethanolaminate catalyst [O⊂Cu4{N(CH2CH2O)3}4(BOH)4][BF4]2 (1), aqueous hydrogen peroxide, acetonitrile solvent and an acid promoter (co-catalyst), have been investigated based on the combination of experimental kinetic, selectivity, ESR and UV–vis methods. The nature of acid promoter (hydrochloric, sulfuric, nitric and trifluoroacetic acid) is shown to be a key factor affecting significantly the rate of alkane oxidation. Although all these acids exhibit noticeable promoting effect, it has been observed that in the presence of HCl the reaction proceeds extremely rapidly, being one order faster than those promoted by the other acids, and allowing to achieve the remarkably high turnover frequencies (TOFs) of ca. 600 h−1. The unusual rate-accelerating role of water has also been disclosed in the oxidation of cyclohexane catalyzed by 1 + HCl or 1 + CF3COOH systems. Furthermore, uncommon second-order reaction kinetics with respect to the catalyst have been found. A mechanism of the alkane oxygenation has been proposed, which includes the formation of hydroxyl radicals attacking the alkane molecule. Hydroxyl radicals are formed via the interaction between H2O2 and catalytically active Cu(I) species, the latter being reversibly generated from 1 under the action of an acid, H2O2 and water.

Kirillova M.V. , Kozlov Y.N. , Shulʹpina L.S. , Lyakin O.Y. , Kirillov A.M. , Talzi E.P. , Pombeiro A.J.L. , Shulʹpin G.B.
Remarkably Fast Oxidation of Alkanes by Hydrogen Peroxide Catalyzed by a Tetracopper(II) Triethanolaminate Complex: Promoting Effects of Acid Co-Catalysts and Water, Kinetic and Mechanistic Features
Journal of Catalysis. 2009. V.268. N1. P.26-38. DOI: 10.1016/j.jcat.2009.08.016 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	15 июн. 2009 г.
Принята к публикации:	29 авг. 2009 г.
Опубликована online:	29 сент. 2009 г.
Опубликована в печати:	15 нояб. 2009 г.

Web of science:	WOS:000272349000004
Scopus:	2-s2.0-71549139793
РИНЦ:	15299337
Chemical Abstracts:	2009:1351125
Chemical Abstracts (print):	152:144137
OpenAlex:	W1980833468

БД	Цитирований
Web of science	124
Scopus	121
РИНЦ	127
OpenAlex	131