Iron-oxygen intermediates in catalyst systems non-heme Fe complex/H2O2(AcOOH)/RC(O)OH and their reactivity in oxidative dearomatization reactions

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 , E-ISSN: 1879-0259

Output data

Year: 2025, Volume: 179, Article number : 114687, Pages count : DOI: 10.1016/j.inoche.2025.114687

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

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. 114687 . DOI: 10.1016/j.inoche.2025.114687 WOS Scopus OpenAlex

Web of science:	WOS:001499376200003
Scopus:	2-s2.0-105005652168
OpenAlex:	W4410396887

DB	Citing
Scopus	Нет цитирований
OpenAlex	Нет цитирований