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

doi:10.1021/jacs.1c03358

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

Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

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 language	English
Pages (from-to)	15556-15561
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	143
Issue number	38
DOIs	https://doi.org/10.1021/jacs.1c03358
State	Published - 29 Sep 2021

Bibliographical note

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.

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10.1021/jacs.1c03358

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@article{dc3fbc6a4de7420fb45d2c27febf8db2,

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

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, M{\"o}ssbauer, 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.",

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

note = "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: {\textcopyright} 2021 American Chemical Society.",

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doi = "10.1021/jacs.1c03358",

language = "English",

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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.

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U2 - 10.1021/jacs.1c03358

DO - 10.1021/jacs.1c03358

M3 - Article

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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 -

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

Abstract

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