Reductive Cleavage of Nitrite to Form Terminal Uranium Mono-Oxo Complexes

Uranium terminal mono-oxo complexes are prepared with a unique activation of nitrite following reductive cleavage of an N–O bond with loss of nitric oxide. The thermodynamic driving force of UO bond formation differentiates this reactivity from known mechanisms of nitrite reduction, which are typically mediated by proton transfer. Mechanistic details are explored by DFT supporting a simple homolytic cleavage pathway from a κ1–ONO bound intermediate. Complexes of the formula UVIOX­[N­(SiMe3)2]3 are formed providing a trigonal bipyramidal framework into which ligands trans to the UO bond may be installed.