On the Formation of "Hypercoordinated" Uranyl Complexes

TitleOn the Formation of "Hypercoordinated" Uranyl Complexes
Publication TypeJournal Article
Year of Publication2011
AuthorsSchoendorff G, de Jong WA, Van Stipdonk MJ, Gibson JK, Rios D, Gordon MS, Windus TL
Journal TitleInorganic Chemistry
Date Published09/05
Type of ArticleArticle
ISBN Number0020-1669
Accession NumberWOS:000294242700072
Keywordsdensity, energy-adjusted pseudopotentials, EXCHANGE, nwchem, parameter sets, THERMOCHEMISTRY

Recent gas-phase experimental studies suggest the presence of hypercoordinated uranyl complexes. Coordination of acetone (Ace) to uranyl to form hypercoordinated species is examined using density functional theory (DFT) with a range of functionals and second-order perturbation theory (MP2). Complexes with up to eight acetones were studied. It is shown that no more than six acetones can bind directly to uranium and that the observed uranyl complexes are not hypercoordinated. In addition, other more exotic species involving proton transfer between acetones and species involving enol tautomers of acetone are high-energy species that are unlikely to form.

Alternate JournalInorg. Chem.