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

Abstract The use of CH 4 and CO 2 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 CH 4 with CO 2 under thermal collision conditions to produce ketene (H 2 C=C=O), an important intermediate in synthetic chemistry. The order to feed the reactants (CH 4 and CO 2 ) is important and CH 4 should be firstly fed to produce the C 2 product. Molecular‐level mechanisms including control of product selectivity have been revealed for coupling of CH 4 with CO 2 under mild conditions.