Aromatic hydroxylation of anthracene derivatives by a chromium(iii)-superoxo complex via proton-coupled electron transfer
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Devi, Tarali
[1
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Lee, Yong-Min
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Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South KoreaEwha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Lee, Yong-Min
[1
]
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Nam, Wonwoo
[1
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Fukuzumi, Shunichi
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Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, JapanEwha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Fukuzumi, Shunichi
[1
,2
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[1] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
[2] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan
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(O-2)](+) (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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Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South KoreaEwha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Lee, Yong-Min
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Nam, Wonwoo
Fukuzumi, Shunichi
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Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, JapanEwha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
机构:
Ewha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South KoreaEwha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Devi, Tarali
Lee, Yong-Min
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Ewha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South KoreaEwha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Lee, Yong-Min
Fukuzumi, Shunichi
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Ewha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, JapanEwha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Fukuzumi, Shunichi
Nam, Wonwoo
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Ewha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
Ningbo Univ, Inst Drug Discovery Technol, Ningbo 315211, Peoples R ChinaEwha Woman Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
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Univ Paris Diderot, Electrochim Mol Lab, CNRS, Unite Mixte Rech 7591, F-75205 Paris 13, FranceUniv Paris Diderot, Electrochim Mol Lab, CNRS, Unite Mixte Rech 7591, F-75205 Paris 13, France