On the Formation of “Hypercoordinated” Uranyl Complexes

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2011-08-01
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de Jong, Wibe
Van Stipdonk, Michael
Rios, Daniel
Gordon, Mark
Windus, Theresa
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Windus, Theresa
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Ames National LaboratoryChemistry
Abstract

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.

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Reprinted (adapted) with permission from Inorganic Chemistry 50 (2011): 8490, doi:10.1021/ic201080z. Copyright 2011 American Chemical Society.

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Sat Jan 01 00:00:00 UTC 2011
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