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.