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Regioselective Oxybromination of Benzene and Its Derivatives by Bromide Anion with a Mononuclear Nonheme Mn(IV)-Oxo Complex
- Regioselective Oxybromination of Benzene and Its Derivatives by Bromide Anion with a Mononuclear Nonheme Mn(IV)-Oxo Complex
- Sharma, Namita; Lee, Yong-Min; Li, Xiao-Xi; Nam, Wonwoo; Fukuzumi, Shunichi
- Ewha Authors
- 남원우; 이용민; Shunichi Fukuzumi
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi
- Issue Date
- Journal Title
- INORGANIC CHEMISTRY
- INORGANIC CHEMISTRY vol. 58, no. 21, pp. 14299 - 14303
- AMER CHEMICAL SOC
- SCI; SCIE; SCOPUS
- Document Type
- Oxybromination of aromatic compounds by high-valent metal-oxo intermediates has yet to be explored despite extensive studies on the oxybromination of aliphatic C-H bonds of hydrocarbons. Herein, we report the regioselective oxybromination of methoxy-substituted benzenes by a nonheme Mn-IV-oxo complex binding scandium ions, [(Bn-TPEN)Mn-IV(O)](2+)-(SC-(OTf3)(2) (1), in the presence of tetrabutylammonium bromide. The regioselective oxybromination occurs at the carbon atom with the highest positive charge via electron transfer (ET) from the methoxy-substituted benzenes to 1. ET driving force dependence of the rate constants of ET from methoxy-substituted benzenes to 1 is well fitted in light of the Marcus theory of ET. Under photo-irradiation, the oxybromination of benzene by 1 can be achieved via ET from benzene to the photoexcited state of 1, although no reaction occurs between benzene and the ground state of 1 in the dark. To the best of our knowledge, this is the first example of reporting the stoichiometric regioselective oxybromination of the benzene ring by a synthetic high-valent Mn(IV)-oxo complex and the catalytic regioselective oxybromination reaction with a Mn(II) complex and a terminal oxidant.
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