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.