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A Mononuclear Non-heme Iron(III)-Peroxo Complex with an Unprecedented High O-O Stretch and Electrophilic Reactivity
- Title
- A Mononuclear Non-heme Iron(III)-Peroxo Complex with an Unprecedented High O-O Stretch and Electrophilic Reactivity
- Authors
- Zhu, Wenjuan; Jang, Semin; Xiong, Jin; Ezhov, Roman; Li, Xiao-Xi; Kim, Taeyeon; Seo, Mi Sook; Lee, Yong-Min; Pushkar, Yulia; Sarangi, Ritimukta; Guo, Yisong; Nam, Wonwoo
- Ewha Authors
- 남원우; 이용민; 서미숙
- SCOPUS Author ID
- 남원우; 이용민; 서미숙
- Issue Date
- 2021
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- ISSN
- 0002-7863
1520-5126
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 143, no. 38, pp. 15556 - 15561
- Publisher
- AMER CHEMICAL SOC
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- A mononuclear non-heme iron(III)-peroxo complex, [Fe(III)(O-2)(13-TMC](+) (1), was synthesized and characterized spectroscopically; the characterization with electron paramagnetic resonance, Mossbauer, X-ray absorption, and resonance Raman spectroscopies and mass spectrometry supported a high-spin S = 5/2 Fe(III) species binding an O-2 unit. A notable observation was an unusually high nu(O-O) at similar to 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 rho 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 rho 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 nu(O-O) value and unprecedented electrophilic reactivity in oxidation reactions.
- DOI
- 10.1021/jacs.1c03358
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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