title: Roles of acetone and diacetone alcohol in coordination and dissociation reactions of uranyl complexes.
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 "[UO(2)(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).
authors.affiliation: Chemical Sciences Division, The Glenn T. Seaborg Center, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
authors.forename: Daniel
authors.initials: D
authors.lastname: Rios
authors.forename: George
authors.initials: G
authors.lastname: Schoendorff
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Van Stipdonk
authors.forename: Mark S
authors.initials: MS
authors.lastname: Gordon
authors.forename: Theresa L
authors.initials: TL
authors.lastname: Windus
authors.forename: John K
authors.initials: JK
authors.lastname: Gibson
authors.forename: Wibe A
authors.initials: WA
authors.lastname: de Jong
mesh_terms: D000096:Acetone / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D000439:Pentanols / Q000737:chemistry*; D010422:Pentanones / Q000737:chemistry*; D011789:Quantum Theory; D014501:Uranium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D000439:Pentanols; D010422:Pentanones; D000096:Acetone; D014501:Uranium; C080344:diacetone alcohol