TY - JOUR
T1 - A Mononuclear Non-heme Iron(III)-Peroxo Complex with an Unprecedented High O-O Stretch and Electrophilic Reactivity
AU - Zhu, Wenjuan
AU - Jang, Semin
AU - Xiong, Jin
AU - Ezhov, Roman
AU - Li, Xiao Xi
AU - Kim, Taeyeon
AU - Seo, Mi Sook
AU - Lee, Yong Min
AU - Pushkar, Yulia
AU - Sarangi, Ritimukta
AU - Guo, Yisong
AU - Nam, Wonwoo
N1 - Funding Information:
This work was supported by the NRF of Korea (NRF-2021R1A3B1076539 to W.N. and NRF-2020R1I1A1A01074630 to Y.-M.L.). This research was also supported by NSF (CHE-2004147 to Y.P. and CHE-1654060 to Y.G.). The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research and by the National Institutes of Health, National Institute of General Medical Sciences (P30GM133894). W.Z. thanks the China Scholarship Council (CSC201908360192).
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/9/29
Y1 - 2021/9/29
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85115953119&partnerID=8YFLogxK
U2 - 10.1021/jacs.1c03358
DO - 10.1021/jacs.1c03358
M3 - Article
C2 - 34529428
AN - SCOPUS:85115953119
SN - 0002-7863
VL - 143
SP - 15556
EP - 15561
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 38
ER -