Catalytic Non-Oxidative Coupling of Methane on Ta₈O₂⁺

, which is a prospective reaction for the generation of valuable chemicals on an industrial scale. Systematic variation of the reaction conditions and the isotopic labeling of methane by deuterium allow for an unambiguous identification of a catalytic cycle. Comparison with the proposed catalytic cycle for tantalum-doped silica catalysts reveals surprising similarities as the mechanism of the C-C coupling step, but also peculiar differences like the mechanism of the eventual formation of molecular hydrogen and ethane. Therefore, this work not only supplies insights into the mechanisms of methane coupling reactions but also illustrates how the study of trapped ionic catalysts can contribute to the understanding of reactions, which are otherwise difficult to study.