A Mononuclear Non-heme Iron(III)-Peroxo Complex with an Unprecedented High O-O Stretch and Electrophilic Reactivity

Wenjuan Zhu, Semin Jang, Jin Xiong, Roman Ezhov, Xiao Xi Li, Taeyeon Kim, Mi Sook Seo, Yong Min Lee, Yulia Pushkar, Ritimukta Sarangi, Yisong Guo, Wonwoo Nam

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Abstract

A mononuclear non-heme iron(III)-peroxo complex, [Fe(III)(O2)(13-TMC)]+ (1), was synthesized and characterized spectroscopically; the characterization with electron paramagnetic resonance, Mössbauer, X-ray absorption, and resonance Raman spectroscopies and mass spectrometry supported a high-spin S = 5/2 Fe(III) species binding an O2 unit. A notable observation was an unusually high νO-O at ∼1000 cm-1 for the peroxo ligand. With regard to reactivity, 1 showed electrophilic reactivity in H atom abstraction (HAA) and O atom transfer (OAT) reactions. In the HAT reaction, a kinetic isotope effect (KIE) value of 5.8 was obtained in the oxidation of 9,10-dihydroanthracene. In the OAT reaction, a negative ρ value of -0.61 in the Hammett plot was determined in the oxidation of p-X-substituted thioanisoles. Another interesting observation was the electrophilic reactivity of 1 in the oxidation of benzaldehyde derivatives, such as a negative ρ value of -0.77 in the Hammett plot and a KIE value of 2.2. To the best of our knowledge, the present study reports the first example of a mononuclear non-heme iron(III)-peroxo complex with an unusually high νO-O value and unprecedented electrophilic reactivity in oxidation reactions.

Original languageEnglish
Pages (from-to)15556-15561
Number of pages6
JournalJournal of the American Chemical Society
Volume143
Issue number38
DOIs
StatePublished - 29 Sep 2021

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