EPR Spectroscopic Detection of the Elusive Fe V ═O Intermediates in Selective Catalytic Oxofunctionalizations of Hydrocarbons Mediated by Biomimetic Ferric Complexes | Sciact - CRIS-система Института катализа

EPR Spectroscopic Detection of the Elusive Fe V ═O Intermediates in Selective Catalytic Oxofunctionalizations of Hydrocarbons Mediated by Biomimetic Ferric Complexes Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2015, Том: 5, Номер: 5, Страницы: 2702-2707 Страниц : 6 DOI: 10.1021/acscatal.5b00169

Ключевые слова

bioinspired catalysis, enantioselective epoxidation, EPR, iron, mechanism

Авторы

Lyakin Oleg Y. ^1,2 , Zima Alexandra M. ^1,2 , Samsonenko Denis G. ^1,3 , Bryliakov Konstantin P. ^1,2 , Talzi 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
3	Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk 630090, Russian Federation

Информация о финансировании (1)

Российский научный фонд

14-13-00158

Herein, we report the EPR spectroscopic study of the bioinspired catalyst systems for selective hydrocarbon oxofunctionalizations based on dinuclear ferric complexes with TPA* and PDP* aminopyridine ligands , hydrogen peroxide and acetic acid (TPA* = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine, PDP* = bis(3,5-dimethyl-4-methoxypyridylmethyl)-(S,S)-2,2'-bipyrrolidine). Using very low temperatures −75 to −85 °C, the extremely unstable and reactive iron-oxygen intermediates, directly reacting with olefins even at −85 °C have been detected for the first time. Their EPR parameters (g1 = 2.070-2.071, g2 = 2.005-2.008, g3 = 1.956-1.960) were very similar to those of the known oxoiron(V) complex [(TMC)FeV=O(NC(O)CH3)]+ (g1 = 2.053, g2 = 2.010, g3 = 1.971, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). On the basis of EPR and reactivity data, the detected intermediates were assigned to the FeV=O active oxidizing species of the catalyst systems studied.

Lyakin O.Y. , Zima A.M. , Samsonenko D.G. , Bryliakov K.P. , Talzi E.P.
EPR Spectroscopic Detection of the Elusive Fe V ═O Intermediates in Selective Catalytic Oxofunctionalizations of Hydrocarbons Mediated by Biomimetic Ferric Complexes

ACS Catalysis. 2015. V.5. N5. P.2702-2707. DOI: 10.1021/acscatal.5b00169 WOS Scopus РИНЦ CAPlusCA OpenAlex

Полный текст от издателя

Поступила в редакцию:	27 янв. 2015 г.
Опубликована online:	26 мар. 2015 г.
Опубликована в печати:	1 мая 2015 г.

Web of science:	WOS:000354012200002
Scopus:	2-s2.0-84929457621
РИНЦ:	24033066
Chemical Abstracts:	2015:510512
Chemical Abstracts (print):	162:514072
OpenAlex:	W2079255657

БД	Цитирований
Web of science	83
Scopus	85
РИНЦ	86
OpenAlex	90