Bioinspired Oxidation of Methane in the Confined Spaces of Molecular Cages

Non-heme iron, vanadium, and copper complexes bearing hemicryptophane cavities were evaluated in the oxidation of methane in water by hydrogen peroxide. According to ¹H nuclear magnetic resonance studies, a hydrophobic hemicryptophane cage accommodates a methane molecule in the proximity of the oxidizing site, leading to an improvement in the efficiency and selectivity for CH₃OH and CH₃OOH compared to those of the analogous complexes devoid of a hemicryptophane cage. While copper complexes showed low catalytic efficiency, their vanadium and iron counterparts exhibited higher turnover numbers, ≤13.2 and ≤9.2, respectively, providing target primary oxidation products (CH₃OH and CH₃OOH) as well as over-oxidation products (HCHO and HCOOH). In the case of caged vanadium complexes, the confinement effect was found to improve either the selectivity for CH₃OH and CH₃OOH (≤15%) or the catalytic efficiency. The confined space of the hydrophobic pocket of iron-based supramolecular complexes plays a significant role in the improvement of both the selectivity (≤27% for CH₃OH and CH₃OOH) and the turnover number of methane oxidation. These results indicate that the supramolecular approach is a promising strategy for the development of efficient and selective bioinspired catalysts for the mild oxidation of methane to methanol.