A Mononuclear Non-heme Iron(III)-Peroxo Complex with an Unprecedented High O-O Stretch and Electrophilic Reactivity
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Zhu, Wenjuan; Jang, Semin; Li, Xiao-Xi; Kim, Taeyeon; Seo, Mi Sook; Lee, Yong-Min; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Xiong, Jin; Guo, Yisong] Carnegie Mellon Univ, Dept Chem, 4400 5th Ave, Pittsburgh, PA 15213 USA; [Ezhov, Roman; Pushkar, Yulia] Purdue Univ, Dept Phys & Astron, W Lafayette, IN 47907 USA; [Nam, Wonwoo] Univ Jinan, Sch Chem & Chem Engn, Jinan 250022, Peoples R China; [Sarangi, Ritimukta] SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Stanford, CA 94025 USA
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2021
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000183645
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/jacs.1c03358
- PubMed https://pubmed.ncbi.nlm.nih.gov/34529428
초록/요약
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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