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

A matter of spin: The [NbN]⁺/[ONbN]⁺ system catalyzes the oxidation of CO through N₂O. In contrast, in the [Nb]⁺/[NbO]⁺ and [NbO]⁺/[Nb(O)₂]⁺ systems, [Nb]⁺ and [NbO]⁺ are oxidized by N₂O, even though neither [NbO]⁺ nor [Nb(O)₂]⁺ react with CO at room temperature. The origins of the distinctly different reactivities are addressed by quantum chemical calculations.

Abstract

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