Production and collision-induced dissociation of gas-phase, water- and alcohol-coordinated uranyl complexes containing halide or perchlorate anions

Victor Anbalagan; Winnie Chien; Garold L Gresham; Gary S Groenewold; Michael J Van Stipdonk

doi:10.1002/rcm.1726

Production and collision-induced dissociation of gas-phase, water- and alcohol-coordinated uranyl complexes containing halide or perchlorate anions

Rapid Commun Mass Spectrom. 2004;18(24):3028-34. doi: 10.1002/rcm.1726.

Authors

Victor Anbalagan¹, Winnie Chien, Garold L Gresham, Gary S Groenewold, Michael J Van Stipdonk

Affiliation

¹ Department of Chemistry, Wichita State University, Wichita, KS 67260-0051, USA.

PMID: 15536628
DOI: 10.1002/rcm.1726

Abstract

Electrospray ionization was used to generate mono-positive gas-phase complexes of the general formula [UO2A(S)n]+ where A = OH, Cl, Br, I or ClO4, S = H2O, CH3OH or CH3CH2OH, and n = 1-3. The multiple-stage dissociation pathways of the complexes were then studied using ion-trap mass spectrometry. For H2O-coordinated cations, the dissociation reactions observed included the elimination of H2O ligands and the loss of HA (where A = Cl, Br or I). Only for the Br and ClO4 versions did collision-induced dissociation (CID) of the hydrated species generate the bare, uranyl-anion complexes. CID of the chloride and iodide versions led instead to the production of uranyl hydroxide and hydrated UO2+. Replacement of H2O ligands by alcohol increased the tendency to eliminate HA, consistent with the higher intrinsic acidity of the alcohols compared to water and potentially stronger UO2-O interactions within the alkoxide complexes compared to the hydroxide version.