Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism

Yiran Kang; Xiao Xi Li; Kyung Bin Cho; Wei Sun; Chungu Xia; Wonwoo Nam; Yong Wang

doi:10.1021/jacs.7b03310

Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism

Yiran Kang, Xiao Xi Li, Kyung Bin Cho, Wei Sun, Chungu Xia, Wonwoo Nam, Yong Wang

Department of Chemistry & Nanoscience

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

42 Scopus citations

Abstract

Although nonheme iron(III)-iodosylarene complexes present amazing oxidative efficiency and selectivity, the nature of such complexes and related oxidation mechanism are still unsolved after decades of experimental efforts. Density functional calculations were employed to explore the structure-reactivity relationship of the iron(III)-iodosylbenzene complex, [Fe^III(tpena^-) (PhIO)]²⁺ (1), in thioanisole sulfoxidation. Our theoretical work revealed that complex 1 can evolve into two resonance valence-bond electronic structures (a high-valent iron-oxo species and a monomeric PhIO species) in thioanisole sulfoxidation to present different reaction mechanisms (the novel bond-cleavage coupled electron transfer mechanism or the direct oxygen-atom transfer mechanism) as a response to different substrate attack orientations.

Original language	English
Pages (from-to)	7444-7447
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	22
DOIs	https://doi.org/10.1021/jacs.7b03310
State	Published - 7 Jun 2017

Bibliographical note

Funding Information:
The authors acknowledge financial support from National Natural Science Foundation of China to Y.W. (grants 21003116 and 21173211) and to W.S. (grant no. 21473226), the NRF of Korea through the CRI (NRF-2012R1A3A2048842) and GRL (NRF-2010-00353) to W.N and MSIP (2013R1A1A2062737) to K.-B.C.).

Publisher Copyright:
© 2017 American Chemical Society.

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10.1021/jacs.7b03310

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title = "Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism",

abstract = "Although nonheme iron(III)-iodosylarene complexes present amazing oxidative efficiency and selectivity, the nature of such complexes and related oxidation mechanism are still unsolved after decades of experimental efforts. Density functional calculations were employed to explore the structure-reactivity relationship of the iron(III)-iodosylbenzene complex, [FeIII(tpena-) (PhIO)]2+ (1), in thioanisole sulfoxidation. Our theoretical work revealed that complex 1 can evolve into two resonance valence-bond electronic structures (a high-valent iron-oxo species and a monomeric PhIO species) in thioanisole sulfoxidation to present different reaction mechanisms (the novel bond-cleavage coupled electron transfer mechanism or the direct oxygen-atom transfer mechanism) as a response to different substrate attack orientations.",

author = "Yiran Kang and Li, {Xiao Xi} and Cho, {Kyung Bin} and Wei Sun and Chungu Xia and Wonwoo Nam and Yong Wang",

note = "Funding Information: The authors acknowledge financial support from National Natural Science Foundation of China to Y.W. (grants 21003116 and 21173211) and to W.S. (grant no. 21473226), the NRF of Korea through the CRI (NRF-2012R1A3A2048842) and GRL (NRF-2010-00353) to W.N and MSIP (2013R1A1A2062737) to K.-B.C.). Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/jacs.7b03310",

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T1 - Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism

AU - Kang, Yiran

AU - Li, Xiao Xi

AU - Cho, Kyung Bin

AU - Sun, Wei

AU - Xia, Chungu

AU - Nam, Wonwoo

AU - Wang, Yong

N1 - Funding Information: The authors acknowledge financial support from National Natural Science Foundation of China to Y.W. (grants 21003116 and 21173211) and to W.S. (grant no. 21473226), the NRF of Korea through the CRI (NRF-2012R1A3A2048842) and GRL (NRF-2010-00353) to W.N and MSIP (2013R1A1A2062737) to K.-B.C.). Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/6/7

Y1 - 2017/6/7

N2 - Although nonheme iron(III)-iodosylarene complexes present amazing oxidative efficiency and selectivity, the nature of such complexes and related oxidation mechanism are still unsolved after decades of experimental efforts. Density functional calculations were employed to explore the structure-reactivity relationship of the iron(III)-iodosylbenzene complex, [FeIII(tpena-) (PhIO)]2+ (1), in thioanisole sulfoxidation. Our theoretical work revealed that complex 1 can evolve into two resonance valence-bond electronic structures (a high-valent iron-oxo species and a monomeric PhIO species) in thioanisole sulfoxidation to present different reaction mechanisms (the novel bond-cleavage coupled electron transfer mechanism or the direct oxygen-atom transfer mechanism) as a response to different substrate attack orientations.

AB - Although nonheme iron(III)-iodosylarene complexes present amazing oxidative efficiency and selectivity, the nature of such complexes and related oxidation mechanism are still unsolved after decades of experimental efforts. Density functional calculations were employed to explore the structure-reactivity relationship of the iron(III)-iodosylbenzene complex, [FeIII(tpena-) (PhIO)]2+ (1), in thioanisole sulfoxidation. Our theoretical work revealed that complex 1 can evolve into two resonance valence-bond electronic structures (a high-valent iron-oxo species and a monomeric PhIO species) in thioanisole sulfoxidation to present different reaction mechanisms (the novel bond-cleavage coupled electron transfer mechanism or the direct oxygen-atom transfer mechanism) as a response to different substrate attack orientations.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 22

ER -

Mutable Properties of Nonheme Iron(III)-Iodosylarene Complexes Result in the Elusive Multiple-Oxidant Mechanism

Abstract

Bibliographical note

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