Biomimetic Activation of Molecular Oxygen with a Combined Metalloporphyrinic Framework and Co‐catalyst Platform. Issue 7 (23rd March 2017)

• Record Type: Journal Article
• Authors: Zhao, Min; Wu, Chuan‐De
• Is Part Of: ChemCatChem. Volume 9:Issue 7(2017)
• Page Start: 1192
• Page End: 1196
• Publication Date: 2017-03-23
• Subjects: biomimetic synthesis -- metalloporphyrins -- metal–organic frameworks -- polyoxometalates -- synergistic catalysis; Catalysis -- Periodicals; 541.39505
• DOI: 10.1002/cctc.201601606
• Languages: English
• ISSNs: 1867-3880

Abstract

Abstract: Cytochromes P450 are powerful biocatalysts that present high catalytic efficiency in the aerobic oxidation of hydrocarbons under mild conditions. Even though metal–organic frameworks (MOFs), consisting of biomimetic metalloporphyrin moieties, are highly active in a number of reactions, they are almost powerless in the aerobic oxidation of inert hydrocarbons under mild conditions. Inspired by the catalytic mechanism of enzymes, we introduce N ‐hydroxyphthalimide (NHPI) as an assistant catalyst to help metalloporphyrinic MOF catalysis, for which NHPI acts as a proton‐ and electron‐transfer mediator. The coupled biomimetic system is efficient in the aerobic oxidation of arylalkanes under mild conditions. The catalytic efficiency is significantly improved if the [WZn{Co(H2 O)}2 (ZnW9 O34 )2 ] 12− polyoxometalate is used as a co‐catalyst. The biomimetic platform exhibits enzyme‐like characters by imitating the structural features, active sites, and catalytic mechanism of enzymes. Abstract : In full site : A combined biomimetic platform, consisting of a metalloporphyrinic framework, N ‐hydroxyphthalimide (NHPI), and a polyoxometalate, exhibits enzyme‐like features in the aerobic oxidation of arylalkanes under mild conditions with very high efficiency, selectivity, and sustainability by imitating the structural features, active sites, and catalytic mechanism of enzymes; yields up to 99 % and a turnover number of 25 600 are realized.