On the Remarkable Role of the Nitrogen Ligand in the Gas‐Phase Redox Reaction of the N₂O/CO Couple Catalyzed by [NbN]+

The thermal gas‐phase catalytic reduction of N₂O by CO, mediated by the transition‐metal nitride cluster ion [NbN]+, has been explored by using FT‐ICR mass spectrometry and complemented by high‐level quantum chemical calculations. In contrast to the [Nb]+/[NbO]+ and [NbO]+/[Nb(O)₂]+ systems, in which the oxidation of [Nb]+ and [NbO]+ with N₂O is facile, but in which neither [NbO]+ nor [Nb(O)₂]+ react with CO at room temperature, the [NbN]+/[ONbN]+ system at ambient temperature mediates the catalytic oxidation of CO. The origins of the distinctly different reactivities upon nitrogen ligation are addressed by quantum chemical calculations.

from A via a.sfakia on Inoreader http://bit.ly/2SGniLt