Aromatic hydroxylation of anthracene derivatives by a chromium(III)-superoxo complex via proton-coupled electron transfer

Tarali Devi; Yong Min Lee; Wonwoo Nam; Shunichi Fukuzumi

doi:10.1039/c9cc03245b

Aromatic hydroxylation of anthracene derivatives by a chromium(III)-superoxo complex via proton-coupled electron transfer

Tarali Devi, Yong Min Lee, Wonwoo Nam, Shunichi Fukuzumi

Chemistry & Nanoscience

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

2 Scopus citations

Abstract

The chemistry of metal-superoxo intermediates started being unveiled in oxidation reactions by enzymes and their synthetic model compounds. However, aromatic hydroxylation reactions by the metal-superoxo species are yet to be demonstrated. In this study, we report for the first time that the hydroxylation of aromatic compounds such as anthracene and its derivatives by a mononuclear nonheme Cr(iii)-superoxo complex, [(Cl)(TMC)Cr^III(O₂)]⁺ (1), occurs in the presence of triflic acid (HOTf) via the rate-determining proton-coupled electron transfer (PCET) from anthracene to 1, followed by a fast further oxidation to give anthraquinone. The rate constants of electron transfer from anthracene derivatives to 1 in the presence of HOTf are well analyzed in light of the Marcus theory of electron transfer.

Original language	English
Pages (from-to)	8286-8289
Number of pages	4
Journal	Chemical Communications
Volume	55
Issue number	57
DOIs	https://doi.org/10.1039/c9cc03245b
State	Published - 2019

Bibliographical note

Funding Information:
This work was supported by a SENTAN project from the Japan Science and Technology Agency (JST) to S. F. and JSPS KAKENHI (No. 16H02268 to S. F.) from MEXT, Japan, and the NRF of Korea through CRI (NRF-2012R1A3A2048842 toW. N.), GRL (NRF-2010- 00353 to W. N.), and the Basic Science Research Program (2017- R1D1A1B03029982 to Y.-M. L. and 2017R1D1A1B03032615 to S. F.).

Publisher Copyright:
© 2019 The Royal Society of Chemistry.

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title = "Aromatic hydroxylation of anthracene derivatives by a chromium(III)-superoxo complex via proton-coupled electron transfer",

abstract = "The chemistry of metal-superoxo intermediates started being unveiled in oxidation reactions by enzymes and their synthetic model compounds. However, aromatic hydroxylation reactions by the metal-superoxo species are yet to be demonstrated. In this study, we report for the first time that the hydroxylation of aromatic compounds such as anthracene and its derivatives by a mononuclear nonheme Cr(iii)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+ (1), occurs in the presence of triflic acid (HOTf) via the rate-determining proton-coupled electron transfer (PCET) from anthracene to 1, followed by a fast further oxidation to give anthraquinone. The rate constants of electron transfer from anthracene derivatives to 1 in the presence of HOTf are well analyzed in light of the Marcus theory of electron transfer.",

author = "Tarali Devi and Lee, {Yong Min} and Wonwoo Nam and Shunichi Fukuzumi",

note = "Funding Information: This work was supported by a SENTAN project from the Japan Science and Technology Agency (JST) to S. F. and JSPS KAKENHI (No. 16H02268 to S. F.) from MEXT, Japan, and the NRF of Korea through CRI (NRF-2012R1A3A2048842 toW. N.), GRL (NRF-2010- 00353 to W. N.), and the Basic Science Research Program (2017- R1D1A1B03029982 to Y.-M. L. and 2017R1D1A1B03032615 to S. F.). Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9cc03245b",

language = "English",

volume = "55",

pages = "8286--8289",

journal = "Chemical Communications",

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publisher = "Royal Society of Chemistry",

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T1 - Aromatic hydroxylation of anthracene derivatives by a chromium(III)-superoxo complex via proton-coupled electron transfer

AU - Devi, Tarali

AU - Lee, Yong Min

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - Funding Information: This work was supported by a SENTAN project from the Japan Science and Technology Agency (JST) to S. F. and JSPS KAKENHI (No. 16H02268 to S. F.) from MEXT, Japan, and the NRF of Korea through CRI (NRF-2012R1A3A2048842 toW. N.), GRL (NRF-2010- 00353 to W. N.), and the Basic Science Research Program (2017- R1D1A1B03029982 to Y.-M. L. and 2017R1D1A1B03032615 to S. F.). Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - The chemistry of metal-superoxo intermediates started being unveiled in oxidation reactions by enzymes and their synthetic model compounds. However, aromatic hydroxylation reactions by the metal-superoxo species are yet to be demonstrated. In this study, we report for the first time that the hydroxylation of aromatic compounds such as anthracene and its derivatives by a mononuclear nonheme Cr(iii)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+ (1), occurs in the presence of triflic acid (HOTf) via the rate-determining proton-coupled electron transfer (PCET) from anthracene to 1, followed by a fast further oxidation to give anthraquinone. The rate constants of electron transfer from anthracene derivatives to 1 in the presence of HOTf are well analyzed in light of the Marcus theory of electron transfer.

AB - The chemistry of metal-superoxo intermediates started being unveiled in oxidation reactions by enzymes and their synthetic model compounds. However, aromatic hydroxylation reactions by the metal-superoxo species are yet to be demonstrated. In this study, we report for the first time that the hydroxylation of aromatic compounds such as anthracene and its derivatives by a mononuclear nonheme Cr(iii)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+ (1), occurs in the presence of triflic acid (HOTf) via the rate-determining proton-coupled electron transfer (PCET) from anthracene to 1, followed by a fast further oxidation to give anthraquinone. The rate constants of electron transfer from anthracene derivatives to 1 in the presence of HOTf are well analyzed in light of the Marcus theory of electron transfer.

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DO - 10.1039/c9cc03245b

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SN - 1359-7345

VL - 55

SP - 8286

EP - 8289

JO - Chemical Communications

JF - Chemical Communications

IS - 57

ER -

Aromatic hydroxylation of anthracene derivatives by a chromium(III)-superoxo complex via proton-coupled electron transfer

Abstract

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