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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, Muniyandi; Jeon, So Hyun; Lee, Yong-Min; Seo, Mi Sook; Ohkubo, Kei; Fukuzumi, Shunichi; Nam, Wonwoo
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민; 서미숙; Kei Okubo
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민; 서미숙; Kei Okubo
- Issue Date
- 2016
- Journal Title
- DALTON TRANSACTIONS
- ISSN
- 1477-9226
1477-9234
- Citation
- DALTON TRANSACTIONS vol. 45, no. 1, pp. 376 - 383
- Publisher
- ROYAL SOC CHEMISTRY
- Indexed
- SCI; SCIE; SCOPUS
- Document Type
- Article
- 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
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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