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A Uranyl Peroxide Dimer in the Gas Phase

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [2];  [1]
  1. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. European Commission, Karlsruhe (Germany). Joint Research Centre
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For this study, the gas-phase uranyl peroxide dimer, [(UO2)2(O2)(L)2]2+ where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO22+ and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO2)2(O)(L)2]2+, which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO2)2(OH)2(L)2]2+. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations. The structures of the observed uranyl dimer were computed, with that of the peroxide of particular interest, as a basis to evaluate the formation of condensed phase uranyl peroxides with bent structures. The computed dihedral angle in [(UO2)2(O2)(L)2]2+ is 145°, indicating a substantial deviation from the planar structure with a dihedral angle of 180°. Energies needed to induce bending in the most elementary gas-phase uranyl peroxide complex, [(UO2)2(O2)]2+, were computed. It was found that bending from the lowest-energy planar structure to dihedral angles up to 140° required energies of <10 kJ/mol. The gas-phase results demonstrate the inherent stability of the uranyl peroxide moiety and support the notion that the uranyl-peroxide-uranyl structural unit is intrinsically planar, with only minor energy perturbations needed to form the bent structures found in studtite and uranyl peroxide nanostructures.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1436151
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 56; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Performance of group additivity methods for predicting the stability of uranyl complexes journal January 2020
Synthesis, structural analysis, and supramolecular assembly of a series of in situ generated uranyl–peroxide complexes with functionalized 2,2′-bipyridine and varied carboxylic acid ligands journal January 2018
Structural and computational characterization of a bridging zwitterionic-amidoxime uranyl complex journal January 2019

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