title: Reductive cleavage of nitrite to form terminal uranium mono-oxo complexes.
abstract: 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 κ(1)-ONO bound intermediate. Complexes of the formula U(VI)OX[N(SiMe(3))(2)](3) are formed providing a trigonal bipyramidal framework into which ligands trans to the U═O bond may be installed.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Lewis
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter