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.