title: Gas phase uranyl activation: formation of a uranium nitrosyl complex from uranyl azide.
abstract: Activation of the oxo bond of uranyl, UO2(2+), was achieved by collision induced dissociation (CID) of UO2(N3)Cl2(-) in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2(-) was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2(-) resulted in the loss of N2 to form UO(NO)Cl2(-), in which the "inert" uranyl oxo bond has been activated. Formation of UO2Cl2(-) via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2(-) complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2(-) complex shows that the side-on bonded NO moiety can be considered as NO(3-), suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2(-) to form UO(NO)Cl2(-) and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2(-) and UO2Cl2(-). The observation of UO2Cl2(-) during CID is most likely due to the absence of an energy barrier for neutral ligand loss.
authors.affiliation: †Chemical Sciences Division, ‡Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
authors.forename: Yu
authors.initials: Y
authors.lastname: Gong
authors.affiliation: †Chemical Sciences Division, ‡Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
authors.forename: Wibe A
authors.initials: WA
authors.lastname: de Jong
authors.affiliation: †Chemical Sciences Division, ‡Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
authors.forename: John K
authors.initials: JK
authors.lastname: Gibson