title: Fragmentation of [Ni(NO3)3](-): A Study of Nickel-Oxygen Bonding and Oxidation States in Nickel Oxide Fragments.
abstract: Gas-phase nickel nitrate anions are known to produce nickel oxide nitrate anions, [NiOx(NO3)y](-) upon fragmentation. The goal of this study was to investigate the properties of nickel oxide nitrate complexes generated by electrospray ionization using a tandem quadrupole mass spectrometer and theoretical calculations. The [Ni(NO3)3](-) ion undergoes sequential NO2(•) elimination to yield [NiO(NO3)2](-) and [NiO2(NO3)](-), followed by elimination of O2. The electronic structure of the nickel oxide core influences decomposition. Calculations indicate electron density from oxygen is delocalized onto the metal, yielding a partially oxidized oxygen in [NiO(NO3)2](-). Theoretical studies suggest the mechanism for O2 elimination from [NiO2(NO3)](-) involves oxygen atom transfer from a nitrate ligand to yield an intermediate, [NiO(O2)(NO2)](-), containing an oxygen radical anion ligand, O(•-), a superoxide ligand, O2(•-), and a nitrite ligand bound to Ni(2+). Electron transfer from superoxide partially reduces both the metal and oxygen and yields the energetically favored [NiO(NO2)](-) + O2 products.
authors.affiliation: Department of Chemistry, The University of Alabama , Tuscaloosa, Alabama 35487, United States.
authors.forename: Thomas H
authors.initials: TH
authors.lastname: Hester
authors.affiliation: Department of Chemistry, The University of Alabama , Tuscaloosa, Alabama 35487, United States.
authors.forename: Rachael M
authors.initials: RM
authors.lastname: Albury
authors.affiliation: Department of Chemistry, The University of Alabama , Tuscaloosa, Alabama 35487, United States.
authors.forename: Carrie Jo M
authors.initials: CJ
authors.lastname: Pruitt
authors.affiliation: Department of Chemistry, The University of Alabama , Tuscaloosa, Alabama 35487, United States.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Goebbert