Untitled

Nguyen-Trung, C.; Palmer, Donald A.; Begun, G. M.; Peiffert, C.; Mesmer, R.E.

doi:10.1023/a:1005197030188

Cited by 97 publications

(129 citation statements)

References 21 publications

Supporting

Mentioning

115

Contrasting

Order By: Relevance

“…Work by Vachet and Callahan [14] has suggested that the nitrate anion, within gas-phase transition metal complexes, is primarily a bidentate ligand. The acceptance of three additional ligands by the uranyl-nitrate ion pair is consistent with a hypothesis that ESI produces a gasphase complex with a pentagonal bipyramidal conformation reminiscent of the structure of uranyl complexes in the solution phase [5][6][7][8][9][10][11]. The fact that the uranylhydroxide containing complex ion, as generated by ESI, also incorporated a maximum of 3 additional H 2 O ligands is therefore interesting.…”

Section: Discussionsupporting

confidence: 76%

“…The solution chemistry of uranium is dominated by the uranyl dication, UO 2 2ϩ , which is known to form complexes with a range of ligands [1]. Specific interaction with solvent will significantly influence the physico-chemical behavior of the uranyl ion and its complexes, and this has motivated investigations of complex composition and stability using infrared spectroscopy and extended X-ray absorption fine structure [5][6][7][8][9][10][11]. Unfortunately, explicit control over the interactions of solvent and nonsolvent ligands with the uranyl ion is difficult, which makes the study of species-dependent uranium behavior complicated.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Elucidation of the collision induced dissociation pathways of water and alcohol coordinated complexes containing the uranyl cation

Stipdonk

Anbalagan

Chien

et al. 2003

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Multiple-stage tandem mass spectrometry was used to characterize the dissociation pathways for complexes composed of (1) the uranyl ion, (2) nitrate or hydroxide, and (3) water or alcohol. The complex ions were derived from electrospray ionization (ESI) ϩ . The abundance of the species was greater than expected based on previous experimental measurements of the (slow) hydration rate for UO 2 ϩ when stored in the ion trap. To account for the production of the hydrated product, a reductive elimination reaction involving reactive collisions with water in the ion trap is proposed. T he speciation and reactivity of uranium is a topic of sustained interest because species-dependent chemistry [1] controls processes ranging from nuclear fuel processing [2] to mobility and fate in the geologic subsurface [3,4]. The solution chemistry of uranium is dominated by the uranyl dication, UO 2 2ϩ , which is known to form complexes with a range of ligands [1]. Specific interaction with solvent will significantly influence the physico-chemical behavior of the uranyl ion and its complexes, and this has motivated investigations of complex composition and stability using infrared spectroscopy and extended X-ray absorption fine structure [5][6][7][8][9][10][11]. Unfortunately, explicit control over the interactions of solvent and nonsolvent ligands with the uranyl ion is difficult, which makes the study of species-dependent uranium behavior complicated. To gain a better understanding of the intrinsic interactions between different uranyl species and solvent, we have begun an investigation of uranyl-anion complexes in the gas phase using ion-trap mass spectrometry (IT-MS). Several recent reports have demonstrated that intrinsic metal and metal complex chemistry can be investigated by the (controlled) addition of reagent gas to an ion trap [12][13][14][15][16][17][18][19][20][21][22], or by way of the presence of H 2 O and other small molecule contaminants within the He bath gas used to collisionally cool ions and improve trapping efficiency [23][24][25]. The reactions of uranium ions in the gas phase have been the subject of several earlier investigations. Studies by , and by Schwarz and coworkers [30] have probed the reactions between U ϩ and UO ϩ and organic compounds such as alkanes and alcohols. Armentrout and Beauchamp [31] investigated the oxidation of U ϩ using small molecules such as O 2 , CO, CO 2 , COS, and

show abstract

Section: Discussionsupporting

confidence: 76%

mentioning

confidence: 99%

Elucidation of the collision induced dissociation pathways of water and alcohol coordinated complexes containing the uranyl cation

Stipdonk

Anbalagan

Chien

et al. 2003

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

show abstract

“…This frequency is shifted to lower wavenumbers upon formation of hydrolysis products or because of complexation of the actinyl ion with appropriate organic or inorganic ligands [41,[46][47][48]. The electronegative ligands in the equatorial plane of the linear actinyl ion weaken the U-O bond resulting in the bathochromic shift in the infrared spectra.…”

Section: Ir Spectra Of the Phosvitin-uranyl Complexes In Aqueous Solumentioning

confidence: 99%

Complexation of U(VI) with highly phosphorylated protein, phosvitinA vibrational spectroscopic approach

Raff

Barkleit

et al. 2010

Journal of Inorganic Biochemistry

View full text Add to dashboard Cite

“…10 At low pH, [UO 2 ] 2+ exists as the solvated dication in solution with weakly complexing anions. 10 Hydrolysis 11,12 at higher solution pH values, or the presence of more strongly coordinating anions, produces uranyl complexes coordinated by one or more anionic ligands. 8,13 The chemical diversity of species has motivated research in vibrational spectroscopy and computational chemistry to understand the coordination and nature of bonding in uranyl complexes containing different ligands because these factors have reactivity and stability implications.…”

Section: Introductionmentioning

confidence: 99%

Infrared Spectroscopy of Discrete Uranyl Anion Complexes

Groenewold¹,

Gianotto²,

McIlwain³

et al. 2007

J. Phys. Chem. A

View full text Add to dashboard Cite

The Free-Electron Laser for Infrared Experiments (FELIX) was used to study the wavelength-resolved multiple photon photodissociation of discrete, gas-phase uranyl (UO22+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands and are comparable to solution-phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm(-1) higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.

show abstract

Untitled

Cited by 97 publications

References 21 publications

Elucidation of the collision induced dissociation pathways of water and alcohol coordinated complexes containing the uranyl cation

Elucidation of the collision induced dissociation pathways of water and alcohol coordinated complexes containing the uranyl cation

Complexation of U(VI) with highly phosphorylated protein, phosvitinA vibrational spectroscopic approach

Infrared Spectroscopy of Discrete Uranyl Anion Complexes

Contact Info

Product

Resources

About