Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

The use of CH₄ and CO₂ to produce value-added chemicals via direct C-C coupling is a challenging chemistry problem because of the inertness of these two molecules. Herein, mass spectrometric experiments and high-level quantum-chemical calculations have identified the first diatomic species (CuB⁺ ) that can couple CH₄ with CO₂ under thermal collision conditions to produce ketene (H₂ C=C=O), an important intermediate in synthetic chemistry. The order to feed the reactants (CH₄ and CO₂ ) is important and CH₄ should be firstly fed to produce the C₂ product. Molecular-level mechanisms including control of product selectivity have been revealed for coupling of CH₄ with CO₂ under mild conditions.