Vibrational spectra of discrete UO22+ halide complexes in the gas phase

Groenewold, Gary S.; Stipdonk, Michael J. Van; Jong, Wibe A. de; Gresham, Garold L.; McIlwain, M.E.

doi:10.1016/j.ijms.2010.06.013

Cited by 26 publications

(51 citation statements)

References 64 publications

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“…CID of the CH 3 COS complex also resulted in CH 3 COSH loss (30%), to yield what can be formally represented as [UO 2 (CH 3 COS)-(CH 2 COS)] − , an intriguing species. In the CID mass spectra of the complexes that yielded [U V O 2 X 2 ] − ions, formation of [U VI O 2 X 2 (O 2 )] − was also observed during the 40 ms period of the CID process (shown for X = NCS in Figure S1 of the Supporting Information).The halide complexes of uranyl(VI) with Cl and Br did not yield any CID product ions under our experimental conditions; interestingly, Groenewold et al 30 observed in IRMPD experiments that [U VI O 2 X 3 ] − complexes eliminated neutral [U VI O 2 X 2 ] for X = Cl and Br and eliminated a halogen radical for X = Br and I. In the present experiments, CID of [U VI O 2 X 3 ] − may similarly result in fragmentation to [U VI O 2 X 2 ] and X − , with the halide anion unobserved due to the low-mass detection limit imposed by the instrumental parameters.…”

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confidence: 63%

“…The halide complexes of uranyl(VI) with Cl and Br did not yield any CID product ions under our experimental conditions; interestingly, Groenewold et al 30 and X − , with the halide anion unobserved due to the low-mass detection limit imposed by the instrumental parameters. CID of the complexes with X = NO 3 and ClO 4 both yielded the oxo species [UO 2 X 2 (O)] − by loss of NO 2 and ClO 3 , respectively; these dissociation channels have been previously observed.…”

Section: ■ Computational Detailsmentioning

confidence: 56%

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Gas-Phase Reactions of Molecular Oxygen with Uranyl(V) Anionic Complexes—Synthesis and Characterization of New Superoxides of Uranyl(VI)

et al. 2015

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Gas-phase complexes of uranyl(V) ligated to anions X(-) (X = F, Cl, Br, I, OH, NO3, ClO4, HCO2, CH3CO2, CF3CO2, CH3COS, NCS, N3), [UO2X2](-), were produced by electrospray ionization and reacted with O2 in a quadrupole ion trap mass spectrometer to form uranyl(VI) anionic complexes, [UO2X2(O2)](-), comprising a superoxo ligand. The comparative rates for the oxidation reactions were measured, ranging from relatively fast [UO2(OH)2](-) to slow [UO2I2](-). The reaction rates of [UO2X2](-) ions containing polyatomic ligands were significantly faster than those containing the monatomic halogens, which can be attributed to the greater number of vibrational degrees of freedom in the polyatomic ligands to dissipate the energy of the initial O2-association complexes. The effect of the basicity of the X(-) ligands was also apparent in the relative rates for O2 addition, with a general correlation between increasing ligand basicity and O2-addition efficiency for polyatomic ligands. Collision-induced dissociation of the superoxo complexes showed in all cases loss of O2 to form the [UO2X2](-) anions, indicating weaker binding of the O2(-) ligand compared to the X(-) ligands. Density functional theory computations of the structures and energetics of selected species are in accord with the experimental observations.

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confidence: 63%

Section: ■ Computational Detailsmentioning

confidence: 56%

Gas-Phase Reactions of Molecular Oxygen with Uranyl(V) Anionic Complexes—Synthesis and Characterization of New Superoxides of Uranyl(VI)

et al. 2015

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“…A scaling factor of 0.98 was applied to the computed DFT frequencies to account for mode anharmonicities and deficiency in the exchangecorrelation functional used. [51][52][53] As is apparent in Fig. 6(a) there is good agreement between the IRMPD spectra and the computational results for the GS isomer.…”

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confidence: 74%

Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation

Jian

et al. 2018

Inorg. Chem.

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The following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization:which spontaneously adds water to yield [UO 2 (12C4-H)-(H 2 O)] + . The latter has the same composition as complex [ U O 2 ( 1 2 C 4 ) ( O H ) ] + p r o d u c e d b y C I D o f [UO 2 (12C4) 2 (OH)] + but exhibits different reactivity with water. The postulated structures as isomeric [UO 2 (12C4-H)(H 2 O)] + and [UO 2 (12C4)(OH)] + were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. The structure of [UO 2 (12C4-H)] + corresponds to cleavage of a C−O bond in the 12C4 ring, with formation of a discrete U−O eq bond and equatorial coordination by three intact ether moieties. Comparison of IRMPD and computed IR spectra furthermore enabled assignment of the structures of the other complexes. Theoretical studies of the chemical bonding features of the complexes provide an understanding of their stabilities and reactivities. The results reveal bonding and structures of the uranyl/12C4 complexes and demonstrate the synthesis and identification of two different isomers of gas-phase uranyl coordination complexes.

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“…To confirm that UO 4 − results from the reaction of UO 2 (C 2 O 4 ) − with O 2 , an excess of isotopically labeled 18 O 2 was introduced into the ion trap. The result is shown in Figure 3, where the dominant product peak at 306 m/ z corresponds to reaction of UO 2 (C 2 O 4 ) − with 18 O 2 to yield UO 2 18 O 2 (unless specified otherwise, O refers to the 99.8% natural abundance 16 O isotope). The minor peak at 304 m/z is attributed to oxo-exchange of UO 2 18 O 2 − with background water in the trap to yield UO 3 18 O − .…”

Section: ■ Computational Methodsmentioning

confidence: 99%

Revealing Disparate Chemistries of Protactinium and Uranium. Synthesis of the Molecular Uranium Tetroxide Anion, UO₄^–

et al. 2017

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The synthesis, reactivity, structures, and bonding in gas-phase binary and complex oxide anion molecules of protactinium and uranium have been studied by experiment and theory. The oxalate ions, AnVO2(C2O4)−, where An = Pa or U, are essentially actinyl ions, AnVO2 +, coordinated by an oxalate dianion. Both react with water to yield the pentavalent hydroxides, AnVO(OH)2(C2O4)−. The chemistry of Pa and U becomes divergent for reactions that result in oxidation: whereas PaVI is inaccessible, UVI is very stable. The UVO2(C2O4)− complex exhibits a remarkable spontaneous exothermic replacement of the oxalate ligand by O2 to yield UO4 – and two CO2 molecules. The structure of the uranium tetroxide anion is computed to correspond to distorted uranyl, UVIO2 2+, coordinated in the equatorial plane by two equivalent O atoms each having formal charges of −1.5 and U–O bond orders intermediate between single and double. The unreactive nature of PaVO2(C2O4)− toward O2 is a manifestation of the resistance toward oxidation of PaV, and clearly reveals the disparate chemistries of Pa and U. The uranium tetroxide anion, UO4 –, reacts with water to yield UO5H2 –. Infrared spectra obtained for UO5H2 – confirm the computed lowest-energy structure, UO3(OH)2 –.

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Vibrational spectra of discrete UO22+ halide complexes in the gas phase

Cited by 26 publications

References 64 publications

Gas-Phase Reactions of Molecular Oxygen with Uranyl(V) Anionic Complexes—Synthesis and Characterization of New Superoxides of Uranyl(VI)

Gas-Phase Reactions of Molecular Oxygen with Uranyl(V) Anionic Complexes—Synthesis and Characterization of New Superoxides of Uranyl(VI)

Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation

Revealing Disparate Chemistries of Protactinium and Uranium. Synthesis of the Molecular Uranium Tetroxide Anion, UO₄^–

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Vibrational spectra of discrete UO22+ halide complexes in the gas phase

Cited by 26 publications

References 64 publications

Gas-Phase Reactions of Molecular Oxygen with Uranyl(V) Anionic Complexes—Synthesis and Characterization of New Superoxides of Uranyl(VI)

Gas-Phase Reactions of Molecular Oxygen with Uranyl(V) Anionic Complexes—Synthesis and Characterization of New Superoxides of Uranyl(VI)

Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation

Revealing Disparate Chemistries of Protactinium and Uranium. Synthesis of the Molecular Uranium Tetroxide Anion, UO4–

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Revealing Disparate Chemistries of Protactinium and Uranium. Synthesis of the Molecular Uranium Tetroxide Anion, UO₄^–