Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation | Sciact - CRIS-система Института катализа

Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation Научная публикация

Журнал

Catalysis Communications
ISSN: 1566-7367 , E-ISSN: 1873-3905

Вых. Данные

Год: 2018, Том: 108, Страницы: 77-81 Страниц : 5 DOI: 10.1016/j.catcom.2018.01.034

Ключевые слова

C–H oxidation, Enzyme models, EPR spectroscopy, Iron, Reaction mechanisms

Авторы

Zima Alexandra M. ^1,2 , Lyakin Oleg Y. ^1,2 , Bryliakov Konstantin P. ^1,2 , Talsi Evgenii P. ^1,2

Организации

1	Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
2	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation

Информация о финансировании (2)

1	Федеральное агентство научных организаций России	0303-2016-0005
2	Российский фонд фундаментальных исследований	17-03-00991

Iron complexes [((S,S)-PDP*)FeIII(μ-OH)2FeIII((S,S)-PDP*)](OTf)4 (6), (S,S)-PDP* = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine, and [(TPA*)FeIII(μ-OH)2FeIII(TPA*)](OTf)4 (7), TPA* = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine, catalyze the selective hydroxylation of alkanes with H2O2 and peroxycarboxylic acids. Using in situ EPR spectroscopy, direct kinetic data on the reactivity of the iron-oxo intermediates formed in the catalyst systems 6,7/oxidant/RCOOH (RCOOH = acetic acid (AA) or 2-ethylhexanoic acid (EHA)) toward cyclohexane have been obtained for the first time, thus corroborating their key role in the selective C–H oxidation. Intermediates 6aAA, 6aEHA and 7a2 EHA with proposed structures [((S,S)-PDP*)FeV[dbnd]O(OC(O)CH3)]2+, [((S,S)-PDP*)FeV[dbnd]O(OC(O)R)]2+ and [(TPA*)FeV[dbnd]O(OC(O)R)]2+ (RCOOH = EHA) display similar EPR spectra (g1 = 2.07, g2 = 2.01, g3 = 1.96) and have close reactivities toward cyclohexane at −70 °C (k2 = 2–3 × 10−3 M−1 s−1).

Zima A.M. , Lyakin O.Y. , Bryliakov K.P. , Talsi E.P.
Direct Reactivity Studies of Non-Heme Iron-Oxo Intermediates Toward Alkane Oxidation
Catalysis Communications. 2018. V.108. P.77-81. DOI: 10.1016/j.catcom.2018.01.034 WOS Scopus РИНЦ CAPlus OpenAlex

Поступила в редакцию:	6 дек. 2017 г.
Принята к публикации:	31 янв. 2018 г.
Опубликована online:	2 февр. 2018 г.
Опубликована в печати:	1 апр. 2018 г.

Web of science:	WOS:000432766800016
Scopus:	2-s2.0-85041401940
РИНЦ:	35484681
Chemical Abstracts:	2018:259966
OpenAlex:	W2793117617

БД	Цитирований
Web of science	17
Scopus	17
РИНЦ	17
OpenAlex	17