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Aerobic catechol oxidation catalyzed by a bis(μ-oxo)dimanganese(III,III) complex via a manganese(II)-semiquinonate complex

Inorganic Chemistry, ISSN: 0020-1669, Vol: 44, Issue: 10, Page: 3473-3478
2005
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Article Description

A 3,5-di-terf-butyl-1,2-semiquinonato (DTBSQ) adduct of Mn(II) was prepared by a reaction between Mn(TPA)Cl (TPA = tris(pyridin-2-ylmethyl)amine) and DTBSQ anion and was isolated as a tetraphenylborate salt. The X-ray crystal structure revealed that the complex is formulated as a manganese(II)-semiquinonate complex [Mn(TPA) (DTBSQ)] (1). The electronic spectra in solution also indicated the semiquinonate coordination to Mn. The exposure of 1 in acetonitrile to dioxygen afforded 3,5-di-tert-butyl-1,2-benzoquione and a bis(μ-oxo)dimanganese(III, III) complex [Mn(μ-oxo)(TPA) ] (2). The reaction of 2 with 3,5-di-terf-butylcatechol (DTBCH) quantitatively afforded two equivalents of 1 under anaerobic conditions. The highly efficient catalytic oxidation of DTBCH with dioxygen was achieved by combining the above two reactions, that is, by constructing a catalytic cycle involving both manganese complexes 1 and 2. It was revealed that dioxygen is reduced to water but not to hydrogen peroxide in the catalytic cycle. © 2005 American Chemical Society.

Bibliographic Details

Hitomi, Yutaka; Ando, Akira; Matsui, Hajime; Ito, Tomoyuki; Tanaka, Tsunehiro; Ogo, Seiji; Funabiki, Takuzo

American Chemical Society (ACS)

Chemistry

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