Reductive disproportionation of nitric oxide mediated by low-valent uranium
Christopher J Hoerger1, Henry S La Pierre, Laurent Maron
1Friedrich-Alexander-University of Erlangen-Nürnberg (FAU), Department of Chemistry and Pharmacy, Inorganic Chemistry, Egerlandstrasse 1, 91058 Erlangen, Germany. karsten.meyer@fau.de.
Abstract:
The reductive disproportionation of nitric oxide (1 atm) is mediated by the bulky U(III) aryloxide [U(III)(OAr(Ad,Ad,Me))3] ((Ad,Ad,Me)ArO = O-C6H2-2,6-Ad-4-Me) (1) to form the U(V) terminal oxo species [((Ad,Ad,Me)ArO)3U(V)(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 η(1)-O bound nitric oxide ligand with gaseous NO to give an η(1)-(N2O2)(1-) intermediate prior to the spontaneous extrusion of N2O to yield the U(V) terminal oxo species 2.
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