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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorLeavitt, Christopher M.en_US
dc.contributor.authorBryantsev, Vyacheslav S.en_US
dc.contributor.authorDe Jong, Wibe A.en_US
dc.contributor.authorDiallo, Mamadou S.en_US
dc.contributor.authorGoddard, William A.en_US
dc.contributor.authorGroenewold, Gary S.en_US
dc.contributor.authorVan Stipdonk, Michael J.en_US
dc.identifier.citationThe journal of physical chemistry. A. 2009 Mar 19; 113(11): 2350-8.en_US
dc.descriptionClick on the DOI link below to access the article.en_US
dc.description.abstractGas-phase complexes of the formula [UO2(lig)]+ (lig = acetone (aco) or dimethylsulfoxide (dmso)) were generated by electrospray ionization (ESI) and studied by tandem ion-trap mass spectrometry to determine the general effect of ligand charge donation on the reactivity of UO2(+) with respect to water and dioxygen. The original hypothesis that addition of O2 is enhanced by strong sigma-donor ligands bound to UO2(+) is supported by results from competitive collision-induced dissociation (CID) experiments, which show near exclusive loss of H2O from [UO2(dmso)(H2O)(O2)]+, whereas both H2O and O2 are eliminated from the corresponding [UO2(aco)(H2O)(O2)]+ species. Ligand-addition reaction rates were investigated by monitoring precursor and product ion intensities as a function of ion storage time in the ion-trap mass spectrometer: these experiments suggest that the association of dioxygen to the UO2(+) complex is enhanced when the more basic dmso ligand was coordinated to the metal complex. Conversely, addition of H2O is favored for the analogous complex ion that contains an aco ligand. Experimental rate measurements are supported by density function theory calculations of relative energies, which show stronger bonds between UO2(+) and O2 when dmso is the coordinating ligand, whereas bonds to H2O are stronger for the aco complex.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesThe journal of physical chemistry. Aen_US
dc.relation.ispartofseriesJ Phys Chem Aen_US
dc.titleAddition of H2O and O2 to acetone and dimethylsulfoxide ligated uranyl(V) dioxocationsen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2009 American Chemical Societyen_US

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