Issue 72, 2016

Reductive disproportionation of nitric oxide mediated by low-valent uranium

Abstract

The reductive disproportionation of nitric oxide (1 atm) is mediated by the bulky UIII aryloxide [UIII(OArAd,Ad,Me)3] (Ad,Ad,MeArO = O-C6H2-2,6-Ad-4-Me) (1) to form the UV terminal oxo species [(Ad,Ad,MeArO)3UV(O)] (2) and N2O, as confirmed by single crystal X-ray diffraction and GC-MS measurements. The reaction is quantitative in the solid state. Mechanistic and theoretical studies of the reaction suggest that the N–N bond is formed by the coupling of an η1-O bound nitric oxide ligand with gaseous NO to give an η1-(N2O2)1− intermediate prior to the spontaneous extrusion of N2O to yield the UV terminal oxo species 2.

Graphical abstract: Reductive disproportionation of nitric oxide mediated by low-valent uranium

Supplementary files

Article information

Article type
Communication
Submitted
28 Jul 2016
Accepted
05 Aug 2016
First published
05 Aug 2016

Chem. Commun., 2016,52, 10854-10857

Reductive disproportionation of nitric oxide mediated by low-valent uranium

C. J. Hoerger, H. S. La Pierre, L. Maron, A. Scheurer, F. W. Heinemann and K. Meyer, Chem. Commun., 2016, 52, 10854 DOI: 10.1039/C6CC06095A

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