Direct Evaluation of the Reactivity of Nonheme Iron(V)–Oxo Intermediates toward Arenes | Sciact - CRIS-система Института катализа

Direct Evaluation of the Reactivity of Nonheme Iron(V)–Oxo Intermediates toward Arenes Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2018, Том: 8, Страницы: 5255-5260 Страниц : 6 DOI: 10.1021/acscatal.8b00661

Ключевые слова

aromatic C−H oxidation; enzyme models; EPR; iron; mechanism

Авторы

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

Организации

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

Информация о финансировании (1)

Российский научный фонд

17-13-01117

The reactivity of nonheme iron(V)–oxo intermediates toward aromatic C–H oxidation at −70 °C has been directly evaluated. The intermediates were generated upon the interaction of the ferric complex [(PDP*)FeIII(μ-OH)2FeIII(PDP*)](OTf)4 (4◊; PDP* = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine) with peracetic acid in the presence of acetic or 2-ethylhexanoic acid. The second-order rate constants (k2) for the reaction of substituted benzenes with iron–oxo intermediates [(PDP*)FeV═O(OC(O)R)]2+ at −70 °C were determined (R = CH3, 3-heptyl). For more electron rich arenes, much higher k2 values were observed, increasing in the order nitrobenzene < acetophenone < chlorobenzene < benzene < toluene, in accordance with the electrophilic aromatic substitution mechanism. The catalytic oxidation of mono- and dialkylbenzenes with H2O2 proceeded with good efficiency (up to 36.5 TN per Fe atom) and high selectivity toward aromatic oxidation products (up to 91%).

Lyakin O.Y. , Zima A.M. , Tkachenko N.V. , Bryliakov K.P. , Talsi E.P.
Direct Evaluation of the Reactivity of Nonheme Iron(V)–Oxo Intermediates toward Arenes
ACS Catalysis. 2018. V.8. P.5255-5260. DOI: 10.1021/acscatal.8b00661 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	16 февр. 2018 г.
Опубликована online:	1 мая 2018 г.
Опубликована в печати:	1 июн. 2018 г.

Web of science:	WOS:000434369600052
Scopus:	2-s2.0-85046545514
РИНЦ:	38607752
Chemical Abstracts:	2018:878336
Chemical Abstracts (print):	170:534480
OpenAlex:	W2801856951

БД	Цитирований
Web of science	35
Scopus	37
РИНЦ	4
OpenAlex	38