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

Journal Inorganic Chemistry Communications
ISSN: 1387-7003
Output data Year: 2025, Volume: 179, Number: Part 1, Article number : 114687, Pages count : 9 DOI: 10.1016/j.inoche.2025.114687
Tags Biomimetic chemistry; C–H Activation; Dearomatization; Intermediates; Iron
Authors Zima Alexandra M. 1 , Babushkin Dmitrii E. 1 , Lyakin Oleg Y. 1 , Bryliakov Konstantin P. 2 , Talsi Evgenii P. 1
Affiliations
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

Funding (1)

1 Ministry of Science and Higher Education of the Russian Federation FWUR-2024-0032

Abstract: 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
Cite: 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 AN OpenAlex
Dates:
Submitted: Nov 7, 2024
Accepted: May 14, 2025
Published online: May 15, 2025
Published print: Sep 1, 2025
Identifiers:
Scopus: 2-s2.0-105005652168
Chemical Abstracts: 2025:1167368
OpenAlex: W4410396887
Citing: Пока нет цитирований
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