Iron-Oxygen Intermediates in Catalyst Systems non-Heme Fe Complex/H2O2(AcOOH)/RC(O)OH and Their Reactivity in Oxidative Dearomatization Reactions | Sciact - CRIS-система Института катализа

Iron-Oxygen Intermediates in Catalyst Systems non-Heme Fe Complex/H2O2(AcOOH)/RC(O)OH and Their Reactivity in Oxidative Dearomatization Reactions Научная публикация

Журнал

Inorganic Chemistry Communications
ISSN: 1387-7003

Вых. Данные

Год: 2025, Том: 179, Номер: Part 1, Номер статьи : 114687, Страниц : 9 DOI: 10.1016/j.inoche.2025.114687

Ключевые слова

Biomimetic chemistry; C–H Activation; Dearomatization; Intermediates; Iron

Авторы

Zima Alexandra M. ¹ , Babushkin Dmitrii E. ¹ , Lyakin Oleg Y. ¹ , Bryliakov Konstantin P. ² , Talsi Evgenii P. ¹

Организации

1	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
2	Zelinsky Insitute of Organic Chemistry, Leninsky Prospect 47, Moscow 119991, Russian Federation

Информация о финансировании (1)

Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)

FWUR-2024-0032

High-valent EPR active iron-oxygen reactive intermediates were monitored in the catalyst systems 1,2/H2O2(AcOOH)/RC(O)OH (1 = [(TPA*)FeIII(μ-OH)2FeIII(TPA*)](OTf)4, TPA* = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine, 2 = [(PDP*)FeIII(μ-OH)2FeIII(PDP*)](OTf)4, PDP* = N,N′-bis(3,5-dimethyl-4-methoxypyridyl-2-methyl)-(S,S)-2,2′-bipyrrolidine, RC(O)OH = acetic acid, 2-ethylhexanoic acid or chloroacetic acid) in CH3CN/CH2Cl2 solvent, without or with additives of 2,2,2-trifluoroethanol or hexafluoroisopropanol. Namely, the oxoiron(V) complexes [(TPA*)FeV=O(OAc)]2+ (4) and [(PDP*)FeV=O(OAc)]2+ (10) were shown to directly react with alkylaromatic substrates, with species 10 being ca. 10 times more reactive than 4. The reactivity of 10 can be further enhanced by either (1) replacing acetic with 2-chloroacetic acid, or (2) by adding strongly hydrogen bond donating 2,2,2-trifluoroethanol or hexafluoroisopropanol. The oxidation of o-xylene follows the electrophilic aromatic substitution mechanism with predominant ipso-attack, followed by 1,2-methyl shift, leading to products of oxidative dearomatization

Zima A.M. , Babushkin D.E. , Lyakin O.Y. , Bryliakov K.P. , Talsi E.P.
Iron-Oxygen Intermediates in Catalyst Systems non-Heme Fe Complex/H2O2(AcOOH)/RC(O)OH and Their Reactivity in Oxidative Dearomatization Reactions
Inorganic Chemistry Communications. 2025. V.179. NPart 1. 114687 :1-9. DOI: 10.1016/j.inoche.2025.114687 Scopus CAPlus OpenAlex

Поступила в редакцию:	7 нояб. 2024 г.
Принята к публикации:	14 мая 2025 г.
Опубликована online:	15 мая 2025 г.
Опубликована в печати:	1 сент. 2025 г.

Scopus:	2-s2.0-105005652168
Chemical Abstracts:	2025:1167368
OpenAlex:	W4410396887

Пока нет цитирований