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A Mononuclear Non-Heme Manganese(III)-Aqua Complex in Oxygen Atom Transfer Reactions via Electron Transfer

Title
A Mononuclear Non-Heme Manganese(III)-Aqua Complex in Oxygen Atom Transfer Reactions via Electron Transfer
Authors
Sharma, NamitaZou, Huai-BoLee, Yong-MinFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우Shunichi Fukuzumi이용민
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus
Issue Date
2021
Journal Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN
0002-7863JCR Link

1520-5126JCR Link
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 143, no. 3, pp. 1521 - 1528
Publisher
AMER CHEMICAL SOC
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
Metal-oxygen complexes, such as metal-oxo [M(O2-)], -hydroxo [M(OH-)], -peroxo [M(O-2(2)-)], -hydroperoxo [M(OOH-], and -superoxo [M(O-2(center dot-))] species, are capable of conducting oxygen atom transfer (OAT) reactions with organic substrates, such as thioanisole (PhSMe) and triphenylphosphine (Ph3P). However, OAT of metal-aqua complexes, [M(OH2)](n+), has yet to be reported. We report herein OAT of a mononuclear non-heme Mn(III)-aqua complex, [(dpaq)-Mn-III(OH2)](2+) (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), to PhSMe and Ph3P derivatives for the first time; it is noted that no OAT occurs from the corresponding Mn(III)-hydroxo complex, [(dpaq)Mn-III(OH)](+) (2), to the substrates. Mechanistic studies reveal that OAT reaction of 1 occurs via electron transfer from 4-methoxythioanisole to 1 to produce the 4-methoxythioanisole radical cation and [(dpaq)Mn-III(OH2)](+), followed by nucleophilic attack of H2O in [(dpaq)Mn-III(OH2)](+) to the 4-methoxythioanisole radical cation to produce an OH adduct radical, 2,4-(MeO)(2)C6H3S center dot(OH)Me, which disproportionates or undergoes electron transfer to 1 to yield methyl 4-methoxyphenyl sulfoxide. Formation of the thioanisole radical cation derivatives is detected by the stopped-flow transient absorption measurements in OAT from 1 to 2,4-dimethoxythioanisole and 3,4-dimethoxythioanisole, being compared with that in the photoinduced electron transfer oxidation of PhSMe derivatives, which are detected by laser-induced transient absorption measurements. Similarly, OAT from 1 to Ph3P occurs via electron transfer from Ph3P to 1, and the proton effect on the reaction rate has been discussed. The rate constants of electron transfer from electron donors, including PhSMe and Ph3P derivatives, to 1 are fitted well by the electron transfer driving force dependence of the rate constants predicted by the Marcus theory of outer-sphere electron transfer.
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DOI
10.1021/jacs.0c11420
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자연과학대학 > 화학·나노과학전공 > Journal papers
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