Roles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes

TitleRoles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes
Publication TypeJournal Article
Year of Publication2012
AuthorsRios D, Schoendorff G, Van Stipdonk MJ, Gordon MS, Windus TL, Gibson JK, de Jong WA
Journal TitleInorganic Chemistry
Volume51
Pages12768-12775
Date Published12
Type of ArticleArticle
ISBN Number0020-1669
Accession NumberWOS:000311772600022
Keywordsdehydration, density, energy-adjusted pseudopotentials, gas-phase, nitrate, parameter sets
Abstract

Combined collision-induced dissociation mass spectrometry experiments with DFT and MP2 calculations were employed to elucidate the molecular structures and energetics of dissociation reactions of uranyl species containing acetone and diacetone alcohol ligands. It is shown that solutions containing diacetone alcohol ligands can produce species with more than five oxygen atoms available for coordination. Calculations confirm that complexes with up to four diacetone alcohol ligands can be energetically stable but that the effective number of atoms coordinating with uranium in the equatorial plane does not exceed five. Water elimination reactions of diacetone alcohol ligands are shown to have two coordination-dependent reaction channels, through formation of mesityl oxide ligands or formation of alkoxide and protonated mesityl oxide species. The present results provide an explanation for the implausible observation of "[UO2(ACO)(6,7,8)](2+)" in and observed water-elimination reactions from purportedly uranyl-acetone complexes (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781).

URL<Go to ISI>://WOS:000311772600022
DOI10.1021/ic3015964
Alternate JournalInorg. Chem.