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- W2980722519 abstract "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 MnIV-oxo complex binding scandium ions, [(Bn-TPEN)MnIV(O)]2+–(Sc(OTf)3)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 photoirradiation, 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." @default.
- W2980722519 created "2019-10-25" @default.
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- W2980722519 date "2019-10-14" @default.
- W2980722519 modified "2023-10-15" @default.
- W2980722519 title "Regioselective Oxybromination of Benzene and Its Derivatives by Bromide Anion with a Mononuclear Nonheme Mn(IV)–Oxo Complex" @default.
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- W2980722519 doi "https://doi.org/10.1021/acs.inorgchem.9b02410" @default.
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