| Abstract: | The thermal gas‐phase reactions of rhenium carbonyl complexes Re(CO)x ]+ (x =0–3) with methane have been explored by using FT‐ICR mass spectrometry complemented by high‐level quantum chemical calculation. While it had been concluded in previous studies that addition of closed‐shell ligands in general decreases the reactivity of metal ions, the current work provides an exception: the previously demonstrated inertness of atomic Re+ towards methane is completely changed upon ligation with CO. Both Re(CO)]+ and Re(CO)2]+ bring about efficient dehydrogenation of the hydrocarbon under ambient conditions. However, addition of a third ligand to form Re(CO)3]+ completely quenches the reactivity. |
