Oxidation of 2-propanol ligands during collision-induced dissociation of a gas-phase uranyl complex

Stipdonk, Michael J. Van; Chien, Winnie; Anbalagan, Victor; Gresham, Garold L.; Groenewold, Gary S.

doi:10.1016/j.ijms.2004.07.007

Cited by 26 publications

(26 citation statements)

References 51 publications

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“…Ions used for calibration are marked with an asterisk in the tables. [18,20,21] and in Chien et al [19], but also more complex positively charged oligomeric species at higher m/z, as well as a number of simple, nitrate-containing, negatively-charged species.…”

Section: Methodsmentioning

confidence: 84%

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry

Pasilis

Somogyi

Herrmann

et al. 2006

J. Am. Soc. Mass Spectrom.

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Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of

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Section: Methodsmentioning

confidence: 84%

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry

Pasilis

Somogyi

Herrmann

et al. 2006

J. Am. Soc. Mass Spectrom.

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“…[9][10][11] Over the last couple of years, Groenewold and co-workers published results of measurements on various uranyl complexes in the gas phase. [12][13][14][15][16][17] These experiments provide the computational chemistry community with a wealth of experimental benchmark data that can be used as a proving ground for the current computational methodologies and to improve upon them. In a series of joint experimental and computational papers 13,[18][19][20][21] it was shown that vibrational stretching frequencies of the actinide species and the relative energetics calculated with density functional theory (DFT) are in good agreement with experimental data.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

2009

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The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, acetaldehyde, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled in the gas phase for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that 5-coordinate complexes are predominant, while 6-coordinate complexes involving propionitrile and acetone ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand, and in general, nitriles bind more strongly to uranyl than carbonyls. Disciplines Chemistry CommentsReprinted (adapted) The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, acetaldehyde, and acetone) ligands to the uranyl dication (UO 2 2+ ) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled in the gas phase for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that 5-coordinate complexes are predominant, while 6-coordinate complexes involving propionitrile and acetone ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand, and in general, nitriles bind more strongly to uranyl than carbonyls.

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“…However, CID of [UO 2 NO 3 (ROH)] + instead caused elimination of HNO 3 to furnish a ligated uranyl‐alkoxide cation. In another study, we found that the uranyl‐2‐propoxide monocation, when coordinated by a single 2‐propanol molecule, mediated the conversion of the neutral alcohol to acetone, and the propoxide ligand to acetaldehyde, during the multiple‐stage CID experiment 4…”

mentioning

confidence: 97%

“…To improve the understanding of intrinsic uranium chemistry, and in particular the chemistry of species in higher oxidation states (i.e. +5, +6), we1–4 and others5 have been exploring the use of electrospray ionization (ESI) to generate mono‐positive uranyl‐ligand cations for subsequent gas‐phase studies. Our focus to date has been on the use of ESI and ion‐trap mass spectrometry (ITMS) to investigate the multiple‐stage collision‐induced dissociation (CID) of coordinated uranium dioxo cations, and the intrinsic tendency of these species to accept neutral ligands such as H 2 O in the gas phase.…”

mentioning

confidence: 99%

Production and collision‐induced dissociation of gas‐phase, water‐ and alcohol‐coordinated uranyl complexes containing halide or perchlorate anions

Anbalagan

Chien

Gresham

et al. 2004

Rapid Comm Mass Spectrometry

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Electrospray ionization was used to generate mono‐positive gas‐phase complexes of the general formula [UO2A(S)n]+ where A = OH, Cl, Br, I or ClO4, S = H2O, CH3OH or CH3CH2OH, and n = 1–3. The multiple‐stage dissociation pathways of the complexes were then studied using ion‐trap mass spectrometry. For H2O‐coordinated cations, the dissociation reactions observed included the elimination of H2O ligands and the loss of HA (where A = Cl, Br or I). Only for the Br and ClO4 versions did collision‐induced dissociation (CID) of the hydrated species generate the bare, uranyl–anion complexes. CID of the chloride and iodide versions led instead to the production of uranyl hydroxide and hydrated UO. Replacement of H2O ligands by alcohol increased the tendency to eliminate HA, consistent with the higher intrinsic acidity of the alcohols compared to water and potentially stronger UO2O interactions within the alkoxide complexes compared to the hydroxide version. Copyright © 2004 John Wiley & Sons, Ltd.

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Oxidation of 2-propanol ligands during collision-induced dissociation of a gas-phase uranyl complex

Cited by 26 publications

References 51 publications

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry

Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

Production and collision‐induced dissociation of gas‐phase, water‐ and alcohol‐coordinated uranyl complexes containing halide or perchlorate anions

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