Biomimetic Activation of Molecular Oxygen with a Combined Metalloporphyrinic Framework and Co‐catalyst Platform

Cytochromes P450 are powerful biocatalysts which present high catalytic efficiency on the aerobic oxidation of hydrocarbons under mild conditions. Even though metal-organic frameworks (MOFs), consisting of biomimetic metalloporphyrin moieties, are highly active on a number of reactions, however, they are almost powerless on 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, in which NHPI acts as a proton- and electron-transfer mediator. The coupled biomimetic system is efficient on the aerobic oxidation of arylalkanes under mild conditions. The catalytic efficiency is significantly improved when polyoxometallate, [WZn{Co(H2O)}2(ZnW9O34)2]12−, 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.