Gas-Phase Uranyl−Nitrile Complex Ions

Stipdonk, Michael J. Van; Chien, Winnie; Bulleigh, Kellis; Wu, Qinghe; Groenewold, Gary S.

doi:10.1021/jp054422c

Cited by 52 publications

(92 citation statements)

References 42 publications

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“…12 The binding energies for these complexes are 26.5 and 23.7 kcal/mol, respectively. This suggests that a ligand addition with a binding energy greater than 23.7 kcal/mol should be observable in mass spectroscopic studies.…”

Section: +mentioning

confidence: 97%

“…[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%

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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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Section: +mentioning

confidence: 97%

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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“…Average values were also used in the case of [UO 2 (Pn) 4 . 9 Again, there is only one instance for which the water ligands outnumber the nitrile ligands.…”

Section: +mentioning

confidence: 99%

“…This effect occurs for ligand additions to both the dicationic and the monocationic species and can explain the large number of dicationic complexes with mainly nitrile ligands observed experimentally. 9 In addition to ligand addition reactions, charge-exchange or hydrolysis reactions of the form of eqs 3 and 4 have been examined. These reactions involve at least two ligands, and water must be one of them.…”

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confidence: 99%

Gas Phase Computational Studies on the Competition between Nitrile and Water Ligands in Uranyl Complexes^†

Schoendorff¹,

Jong²,

Gordon³

et al. 2010

J. Phys. Chem. A

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The gas phase formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands, [UO2(H2O)m(RCN)n]2+, has been studied using density functional theory with a relativistic effective core potential to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to [UO2OH(H2O)m(RCN)n]+ by the loss of either H3O+ or (RCN + H)+ is also examined. It is found that this reaction is competitive with the ligand addition when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involving acetonitrile being the most prevalent. Finally, ligand addition to the monocation shows trends similar to that of the dication with energetic differences being smaller for the addition to the monocation. The gas phase formation of uranyl dicationic complexes containing water and nitrile (acetonitrile, propionitrile, and benzonitrile) ligands,, has been studied using density functional theory with a relativistic effective core potential to account for scalar relativistic effects on uranium. It is shown that nitrile addition is favored over the addition of water ligands. Decomposition of these complexes to+ by the loss of either H 3 O + or (RCN + H) + is also examined. It is found that this reaction is competitive with the ligand addition when the coordination sphere of uranyl is unsaturated. Additionally, this reaction is influenced by the size of the nitrile ligand with reactions involving acetonitrile being the most prevalent. Finally, ligand addition to the monocation shows trends similar to that of the dication with energetic differences being smaller for the addition to the monocation.

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“…Charged uranyl coordination complexes can be formed using electrospray-ionization (ESI), which has proven to be a highly versatile means for introducing these species into the gas phase. Recent research by our group [22][23][24][25][26], that of Moulin [27,28], and Pasilis [29] have demonstrated the great utility of ESI for forming a variety of dioxouranium V and VI complexes. ESI usually produces multiple species, however, complexes of interest can be isolated on the basis of mass-to-charge ratio using selective ion ejection/storage capabilities of a trapped ion mass spectrometer.…”

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confidence: 99%

Variable denticity in carboxylate binding to the uranyl coordination complexes

Groenewold

Jong

Stipdonk

2010

J. Am. Soc. Mass Spectrom.

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Tris-carboxylate complexes of uranyl [UO 2 ] 2ϩ with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transform ion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetato uranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric ϪCO 2 stretches of the monodentate and bidentate acetate, CH 3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the predominant conformer of the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate and two bidentate benzoate ligands.

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Gas-Phase Uranyl−Nitrile Complex Ions

Cited by 52 publications

References 42 publications

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

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

Gas Phase Computational Studies on the Competition between Nitrile and Water Ligands in Uranyl Complexes^†

Variable denticity in carboxylate binding to the uranyl coordination complexes

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Gas-Phase Uranyl−Nitrile Complex Ions

Cited by 52 publications

References 42 publications

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

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

Gas Phase Computational Studies on the Competition between Nitrile and Water Ligands in Uranyl Complexes†

Variable denticity in carboxylate binding to the uranyl coordination complexes

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Gas Phase Computational Studies on the Competition between Nitrile and Water Ligands in Uranyl Complexes^†