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 |
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| 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 |
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| Affiliations |
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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 WOS Scopus AN OpenAlex
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 WOS Scopus AN OpenAlex
Dates:
| Submitted: | Nov 7, 2024 |
| Accepted: | May 14, 2025 |
| Published online: | May 15, 2025 |
| Published print: | Sep 1, 2025 |
Identifiers:
| Web of science: | WOS:001499376200003 |
| Scopus: | 2-s2.0-105005652168 |
| Chemical Abstracts: | 2025:1167368 |
| OpenAlex: | W4410396887 |
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