title: Formation of bare UO2(2+) and NUO(+) by fragmentation of gas-phase uranyl-acetonitrile complexes.
abstract: In a prior study [Van Stipdonk; et al. J. Phys. Chem. A 2006, 110, 959-970], electrospray ionization (ESI) was used to generate doubly charged complex ions composed of the uranyl ion and acetonitrile (acn) ligands. The complexes, general formula [UO2(acn)n](2+), n = 0-5, were isolated in an 3-D quadrupole ion-trap mass spectrometer to probe intrinsic reactions with H2O. Two general reaction pathways were observed: (a) the direct addition of one or more H2O ligands to the doubly charged complexes and (b) charge-exchange reactions. For the former, the intrinsic tendency to add H2O was dependent on the number and type of nitrile ligand. For the latter, charge exchange involved primarily the formation of uranyl hydroxide, [UO2OH](+), presumably via a collision with gas-phase H2O and the elimination of a protonated nitrile ligand. Examination of general ion fragmentation patterns by collision-induced dissociation, however, was hindered by the pronounced tendency to generate hydrated species. In an update to this story, we have revisited the fragmentation of uranyl-acetonitrile complexes in a linear ion-trap (LIT) mass spectrometer. Lower partial pressures of adventitious H2O in the LIT (compared to the 3-D ion trap used in our previous study) minimized adduct formation and allowed access to lower uranyl coordination numbers than previously possible. We have now been able to investigate the fragmentation behavior of these complex ions completely, with a focus on tendency to undergo ligand elimination versus charge reduction reactions. CID can be used to drive ligand elimination to completion to furnish the bare uranyl dication, UO2(2+). In addition, fragmentation of [UO2(acn)](2+) generated [UO2(NC)](+), which subsequently fragmented to furnish NUO(+). Formation of the nitrido by transfer of N from cyanide was confirmed using precursors labeled with (15)N. The observed formation of [UO2(NC)](+) and NUO(+) was modeled by density functional theory.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University , Pittsburgh, Pennsylvania 15282, United States.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Van Stipdonk
authors.forename: Maria del Carmen
authors.initials: Mdel C
authors.lastname: Michelini
authors.forename: Alexandra
authors.initials: A
authors.lastname: Plaviak
authors.forename: Dean
authors.initials: D
authors.lastname: Martin
authors.forename: John K
authors.initials: JK
authors.lastname: Gibson