Base-Assisted Aerobic C-H Oxidation of Alkylarenes with a Murdochite-Type Oxide Mg₆MnO₈ Nanoparticle Catalyst

Heterogeneously catalyzed aerobic oxidative C-H functionalization under mild conditions is a chemical process to obtain desired oxygenated products directly. Nanosized murdochite-type oxide Mg₆MnO₈ (Mg₆MnO₈-MA) was successfully synthesized by the sol-gel method using malic acid. The specific surface area reached up to 104 m² g^-1, which is about 7 times higher than those (2-15 m² g^-1) of Mg₆MnO₈ synthesized by previously reported methods. Mg₆MnO₈-MA exhibited superior catalytic performance to those of other Mn- and Mg-based oxides, including manganese oxides with Mn-O-Mn active sites for the oxidation of fluorene with molecular oxygen (O₂) as the sole oxidant under mild conditions (40 °C). The present catalytic system was applicable to the aerobic oxidation of various substrates. The catalyst could be recovered by simple filtration and reused several times without obvious loss of its high catalytic performance. The correlation between the reactivity and the pK_a of the substrates, basic properties of catalysts, and kinetic isotope effects suggest a basicity-controlled mechanism of hydrogen atom transfer. The ¹⁸O-labeling experiments, kinetics, and mechanistic studies showed that H abstraction of the hydrocarbon proceeds via a mechanism involving O₂ activation. The structure of Mg₆MnO₈ consisting of isolated Mn⁴⁺ species located in a basic MgO matrix plays an important role in the present oxidation.