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On the Remarkable Role of the Nitrogen Ligand in the Gas‐Phase Redox Reaction of the N2O/CO Couple Catalyzed by [NbN]+.
- Source :
-
Angewandte Chemie International Edition . 3/11/2019, Vol. 58 Issue 11, p3635-3639. 5p. - Publication Year :
- 2019
-
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. 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 FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 58
- Issue :
- 11
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 135059126
- Full Text :
- https://doi.org/10.1002/anie.201814460