期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 38, 页码 15556-15561出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c03358
关键词
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资金
- NRF of Korea [NRF-2021R1A3B1076539, NRF-2020R1I1A1A01074630]
- NSF [CHE-2004147, CHE-1654060]
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Institute of General Medical Sciences [P30GM133894]
- China Scholarship Council [CSC201908360192]
In this study, a mononuclear non-heme iron(III)-peroxo complex was synthesized and characterized, showing high nu(O-O) value and unprecedented electrophilic reactivity in oxidation reactions. Various spectroscopic techniques confirmed the unique properties of the complex, including its H atom abstraction and O atom transfer reactivity. Additionally, interesting observations were made in the oxidation of benzaldehyde derivatives, indicating the complex's potential in various oxidation reactions.
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.
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