View : 89 Download: 0

Regioselective Oxybromination of Benzene and Its Derivatives by Bromide Anion with a Mononuclear Nonheme Mn(IV)-Oxo Complex

Title
Regioselective Oxybromination of Benzene and Its Derivatives by Bromide Anion with a Mononuclear Nonheme Mn(IV)-Oxo Complex
Authors
Sharma, NamitaLee, Yong-MinLi, Xiao-XiNam, WonwooFukuzumi, Shunichi
Ewha Authors
남원우이용민Shunichi Fukuzumi
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus
Issue Date
2019
Journal Title
INORGANIC CHEMISTRY
ISSN
0020-1669JCR Link

1520-510XJCR Link
Citation
INORGANIC CHEMISTRY vol. 58, no. 21, pp. 14299 - 14303
Publisher
AMER CHEMICAL SOC
Indexed
SCIE; SCOPUS WOS
Document Type
Article
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 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.
DOI
10.1021/acs.inorgchem.9b02410
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE