Selective C-O Coupling Hidden in the Thermal Reaction of [Al2 CuO5 ]+ with Methane.

The thermal gas-phase reaction of [Al2 CuO5 ]+ with methane has been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. The generation of atomic [Cu]+ from the [Al2 CuO5 ]+ /CH4 couple corresponds to the only reaction channel. Labeling experiments and computational studies strongly suggest that methane activation is indeed involved in the production of [Cu]+ , and generation of CH2 O prevails. Mechanistic aspects and the associated doping effects are discussed.