title: Activation of gas-phase uranyl: from an oxo to a nitrido complex.
abstract: The uranyl moiety, UO2(2+), is ubiquitous in the chemistry of uranium, the most prevalent actinide. Replacing the strong uranium-oxygen bonds in uranyl with other ligands is very challenging, having met with only limited success. We report here uranyl oxo bond activation in the gas phase to form a terminal nitrido complex, a previously elusive transformation. Collision induced dissociation of gas-phase UO2(NCO)Cl2(-) in an ion trap produced the nitrido oxo complex, NUOCl2(-), and CO2. NUOCl2(-) was computed by DFT to have Cs symmetry and a singlet ground state. The computed bond length and order indicate a triple U-N bond. Endothermic activation of UO2(NCO)Cl2(-) to produce NUOCl2(-) and neutral CO2 was computed to be thermodynamically more favorable than NCO ligand loss. Complete reaction pathways for the CO2 elimination process were computed at the DFT level.
authors.affiliation: Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
authors.forename: Yu
authors.initials: Y
authors.lastname: Gong
authors.forename: Valérie
authors.initials: V
authors.lastname: Vallet
authors.forename: Maria del Carmen
authors.initials: Mdel C
authors.lastname: Michelini
authors.forename: Daniel
authors.initials: D
authors.lastname: Rios
authors.forename: John K
authors.initials: JK
authors.lastname: Gibson