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Effect of Brønsted Acid on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C-H and C=C Oxidation Reactions Научная публикация

Журнал Catalysts
ISSN: 2073-4344
Вых. Данные Год: 2022, Том: 12, Номер: 9, Номер статьи : 949, Страниц : 14 DOI: 10.3390/catal12090949
Ключевые слова C-H activation; intermediate; iron; mechanism; non-heme; oxidation
Авторы Zima Alexandra M. 1 , Lyakin Oleg Y. 1 , Bryliakova Anna A. 1 , Babushkin Dmitrii E. 1 , Bryliakov Konstantin P. 1 , Talsi Evgenii P. 1
Организации
1 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, 630090 Novosibirsk, Russia

Информация о финансировании (1)

1 Российский научный фонд 22-13-00225

Реферат: The effect of HClO4 on the reactivity and selectivity of the catalyst systems 1,2/H2O2/AcOH, based on nonheme iron complexes of the PDP families, [(Me2OMePDP)FeIII(μ-OH)2FeIII(MeOMe2PDP)](OTf)4 (1) and [(NMe2PDP)FeIII(μ-OH)2FeIII(NMe2PDP](OTf)4 (2), toward oxidation of benzylideneacetone (bna), adamantane (ada), and (3aR)-(+)-sclareolide (S) has been studied. Adding HClO4 (2–10 equiv. vs. Fe) has been found to result in the simultaneous improvement of the observed catalytic efficiency (i.e., product yields) and the oxidation regio- or enantioselectivity. At the same time, HClO4 causes a threefold increase of the second-order rate constant for the reaction of the key oxygen-transferring intermediate [(Me2OMePDP)FeV=O(OAc)]2+ (1a), with cyclohexane at −70 °C. The effect of strong Brønsted acid on the catalytic reactivity is discussed in terms of the reversible protonation of the Fe=O moiety of the parent perferryl intermediates. © 2022 by the authors.
Библиографическая ссылка: Zima A.M. , Lyakin O.Y. , Bryliakova A.A. , Babushkin D.E. , Bryliakov K.P. , Talsi E.P.
Effect of Brønsted Acid on the Reactivity and Selectivity of the Oxoiron(V) Intermediates in C-H and C=C Oxidation Reactions
Catalysts. 2022. V.12. N9. 949 :1-14. DOI: 10.3390/catal12090949 WOS Scopus РИНЦ CAPlus OpenAlex
Даты:
Поступила в редакцию: 9 авг. 202 г.
Принята к публикации: 22 авг. 2022 г.
Опубликована online: 26 авг. 2022 г.
Опубликована в печати: 1 сент. 2022 г.
Идентификаторы БД:
Web of science: WOS:000857672500001
Scopus: 2-s2.0-85138615780
РИНЦ: 52650505
Chemical Abstracts: 2022:2500650
OpenAlex: W4293659835
Цитирование в БД:
БД Цитирований
Scopus 5
Web of science 5
РИНЦ 5
OpenAlex 5
Альметрики: