Fragmentation of [Ni(NO3)3](-): A Study of Nickel-Oxygen Bonding and Oxidation States in Nickel Oxide Fragments.

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.

Gas-Phase Fragmentation of Aluminum Oxide Nitrate Anions Driven by Reactive Oxygen Radical Ligands.

Gas-phase metal nitrate anions are known to yield a variety of interesting metal oxides upon fragmentation. The aluminum nitrate anion complexes, Al(NO3)4(-) and AlO(NO3)3(-) were generated by electrospray ionization and studied with collision-induced dissociation and energy-resolved mass spectrometry. Four different decomposition processes were observed, the loss of NO3(-), NO3(•), NO2(•), and O2. The oxygen radical ligand in AlO(NO3)3(-) is highly reactive and drives the formation of AlO(NO3)2(-) upon loss of NO3(•), AlO2(NO3)2(-) upon NO2(•) loss, or Al(NO2)(NO3)2(-) upon abstraction of an oxygen atom from a neighboring nitrate ligand followed by loss of O2. The AlO2(NO3)2(-) fragment also undergoes elimination of O2. The mechanism for O2 elimination requires oxygen atom abstraction from a nitrate ligand in both AlO(NO3)3(-) and AlO2(NO3)2(-), revealing the hidden complexity in the fragmentation of these clusters.

Fragmentation of Cr(NO3)4(-): Metal Oxidation upon O(•-) Abstraction.

The decomposition of chromium nitrate anion, Cr(NO3)4(-), was investigated by tandem mass spectrometry. The major fragments correspond to sequential elimination of NO2(•) via O(•-) abstraction from each nitrate ligand to yield CrOn(NO3)(4-n)(-), n = 1-4, products. The metal is oxidized upon the first three O(•-) abstraction reactions to yield the fully oxidized Cr(VI), closed-shell, CrO3(NO3)(-) fragment. A CrO4(-) fragment was detected, but the metal is not further oxidized upon the fourth O(•-) abstraction. Experiment and theory indicate the first three O(•-) abstraction reactions are low energy processes, but the formation of CrO4(-) is considerably higher in energy. Theoretical studies show the 3d electrons in chromium are removed by O(•-) for CrOn(NO3)(4-n)(-), n = 1-3, to yield oxo, O(2-) ligands, but the electron density is replaced by donation from π bonds involving the oxygen lone pairs. Theory predicts a decrease in metal charge for each O(•-) abstraction, opposite the trend expected for oxidation, due to π electron donation from the oxygen atoms.