Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

11-2012

Journal or Book Title

Inorganic Chemistry

Volume

51

Issue

23

First Page

12768

Last Page

12775

DOI

10.1021/ic3015964

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).

Comments

Reprinted (adapted) with permission from Inorg. Chem., 2012, 51 (23), pp 12768–12775 doi:10.1021/ic3015964. Copyright 2012 American Chemical Society

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

Share

COinS