Thermal Dehydrogenation of Methane by [ReN]<sup/>.

The thermal reaction of the diatomic rhenium nitride cation [ReN]+ with methane has been explored using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. Mechanistic aspects of the reaction have been addressed to uncover scenarios for the competitive generation of a methylene and a hydrogen cyanide ligand attached to the rhenium center. The role the nitrogen atom plays in the reactive [ReN]+ /CH4 couple is elucidated, and the cause of the rather different reactivities of [ReN]+ and its lighter congener [MnN]+ is revealed.