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An amphoteric reactivity of a mixed-valent bis(mu-oxo)dimanganese(III,IV) complex acting as an electrophile and a nucleophile

Title
An amphoteric reactivity of a mixed-valent bis(mu-oxo)dimanganese(III,IV) complex acting as an electrophile and a nucleophile
Authors
Sankaralingam, MuniyandiJeon, So HyunLee, Yong-MinSeo, Mi SookOhkubo, KeiFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우Shunichi Fukuzumi이용민서미숙Kei Okubo
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus; 서미숙scopusscopus; Kei Okuboscopus
Issue Date
2016
Journal Title
DALTON TRANSACTIONS
ISSN
1477-9226JCR Link1477-9234JCR Link
Citation
vol. 45, no. 1, pp. 376 - 383
Publisher
ROYAL SOC CHEMISTRY
Indexed
SCI; SCIE; SCOPUS WOS
Abstract
A mixed-valent bis(mu-oxo)dimanganese(III,IV) complex, [(dpaq)Mn-III(O)(2)Mn-IV(dpaq)](+) (1), was prepared by reacting a hydroxomanganese(III) complex, [(dpaq)Mn-III(OH)](+), with hydrogen peroxide in the presence of triethylamine. The mixed-valent bis(mu-oxo)dimanganese(III,IV) complex (1) was well characterised by UV-vis, EPR and CSI-MS techniques. The electrophilic reactivity of 1 was investigated in the oxidation of 2,6-di- tert-butylphenol derivatives by 1, in which the relative rate afforded a good Hammett correlation with a rho value of -1.0. The nucleophilic character of 1 was then investigated in aldehyde deformylation reactions, using 2-phenylpropionaldehyde (2-PPA) and benzaldehyde derivatives as substrates. In contrast to the case of the reaction of 1 with 2,6-di-tert-butylphenol derivatives, a positive rho value of 0.89 was obtained in the Hammett plot, demonstrating that the bis(mu-oxo)-dimanganese(III,IV) complex is an active nucleophilic oxidant. Thus, 1 exhibited an amphoteric reactivity in both electrophilic and nucleophilic oxidative reactions.
DOI
10.1039/c5dt04292e
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자연과학대학 > 화학·나노과학전공 > Journal papers
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