High‐Spin and Low‐Spin Perferryl Intermediates in Fe(PDP)‐Catalyzed Epoxidations | Sciact - CRIS-система Института катализа

High‐Spin and Low‐Spin Perferryl Intermediates in Fe(PDP)‐Catalyzed Epoxidations Научная публикация

Журнал

ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899

Вых. Данные

Год: 2019, Том: 11, Номер: 21, Страницы: 5345-5352 Страниц : 8 DOI: 10.1002/cctc.201900842

Ключевые слова

Enzyme models; epoxidation; 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	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090 (Russia)
2	Novosibirsk State University, Pirogova 2, Novosibirsk 630090 (Russia)

Информация о финансировании (1)

Российский научный фонд

17-13-01117

Two bioinspired hydroxo‐bridged diferric complexes 6 and 7 with N4‐donor ligands of the PDP type (PDP=N,N′‐bis(pyridin‐2‐ylmethyl)‐2,2′‐bipyrrolidine), differing by substituents at the pyridine rings (4‐NMe2 in 7 vs. 3,5‐Me2‐4‐OMe in 6), efficiently catalyze the enantioselective alkene epoxidation with H2O2 and peracetic acid in the presence of a carboxylic acid additive (up to 99 catalyst turnover numbers, TON, toward epoxide, up to 94 % ee). Catalyst systems based on complex 7 display the high‐spin perferryl intermediate 7 aAA (S=3/2, g1, g2=3.69, g3=1.96), whereas catalyst systems based on complex 6 exhibit the low‐spin perferryl intermediate 6 aAA (S=1/2, g1=2.07, g2=2.01, g3=1.96). The S=3/2 and the S=1/2 intermediates directly react with cyclohexene and cyclohexane at low temperatures (−40 °C and −85 °C, respectively). The catalyst systems, exhibiting less reactive intermediate 7 aAA, demonstrate higher enantioselectivity (% ee) in the epoxidation of chalcone. The origin of the unprecedented high‐spin state of the perferryl intermediate is discussed.

Zima A.M. , Lyakin O.Y. , Bryliakov K.P. , Talsi E.P.
High‐Spin and Low‐Spin Perferryl Intermediates in Fe(PDP)‐Catalyzed Epoxidations
ChemCatChem. 2019. V.11. N21. P.5345-5352. DOI: 10.1002/cctc.201900842 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	8 мая 2019 г.
Принята к публикации:	24 июн. 2019 г.
Опубликована online:	2 июл. 2019 г.
Опубликована в печати:	7 нояб. 2019 г.

Web of science:	WOS:000479743500001
Scopus:	2-s2.0-85070323488
РИНЦ:	41640040
Chemical Abstracts:	2019:1459436
Chemical Abstracts (print):	171:505623
OpenAlex:	W2955941875

БД	Цитирований
Scopus	18
Web of science	16
РИНЦ	20
OpenAlex	21