Molecular Uranates: Laser Synthesis of Uranium Oxide Anions in the Gas Phase

Marçalo, Joaquim; Santos, Marta; Matos, António Pires de; Gibson, John K.

doi:10.1021/ic9003998

Cited by 17 publications

(22 citation statements)

References 29 publications

(44 reference statements)

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“…." [24]. We were able to fragment this ion but the only observed decomposition consisted in the loss of oxygen yielding the fragment ion UO 3 Ϫ (U V -containing ion).…”

Section: Resultsmentioning

confidence: 95%

“…It only suggests exclusion of the superoxide structure. In our opinion, for such structure loss of O 2 or formation of O 2 2Ϫ ion, could be expected [24]. The initial possible structures of UO 4 Ϫ presented in Figure 3 were subjected to quantum mechanical calculations.…”

Section: Resultsmentioning

confidence: 99%

“…The species composed of one uranium atom and four oxygen atoms are known, namely UO 4 2 Ϫ ion [19 -21], and the mentioned in the introduction uranyl peroxide UO 2 Ϫ ions on the full scan spectrum, but the ions were not discussed [10]. The ion UO 4 Ϫ was discussed in respect to the oxidation state of uranium and oxygen by Marcalo et al, the authors generated the ion from solid UO 3 by laser ablation (laser desorption/ionization) [24]. At first, it would seem that UO 4 Ϫ contains U VII , however, because uranium has six valence electrons, the oxidation state higher than VI cannot be expected.…”

Section: Resultsmentioning

confidence: 99%

“…Ϫ ion was previously formed in the gas-phase by electrospray ionization from uranyl nitrate [10] and by laser desorption ionization from UO 3 [24]. In this work, UO 4 Ϫ ion was formed by laser desorption/ionization (and subsequent collision induced dissociation) from uranyl nitrate and others uranyl salts.…”

Section: Uomentioning

confidence: 90%

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Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Sokalska

Prussakowska

Hoffmann

et al. 2010

J. Am. Soc. Mass Spectrom.

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The following ions [UO 2 (NO 3 Ϫ were generated from respective salts (UO 2 (NO 3 ) 2 , UO 2 (ClO 4 ) 3 , UO 2 (CH 3 COO) 2 ) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO 4 Ϫ ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U VI compound, in which oxygen atoms bear unpaired electron and negative charge. In the laboratory, the most common uranium compounds are the salts of uranyl (UO 2 2ϩ -U VI -containing cation), e.g., UO 2 (NO 3 ) 2 , UO 2 (CH 3 COO) 2 . Uranium compounds with this element at other oxidation states (other than IV and VI) are also known, however, they are less stable, e.g., the U V species in solutions easily undergo disproportionation reaction to U(IV) and U(VI) [2]. In nature, there are also uranyl peroxides UO 2 (O 2 ), but the respective minerals UO 2 (O 2 )(H 2 O) 2 and UO 2 (O 2 )(H 2 O) 4 do not exist in high abundances [3]. A number of more developed uranyl peroxides were obtained in labs [4 -7].Mass spectrometric studies of uranyl salts (mainly UO 2 (NO 3 ) 2 ) have been reported, first by using FAB (fast atom bombardment) as ionization method [8], and then by electrospray ionization [9 -15]. Most of the studies were performed in the positive ion mode; only Pasilis et al. have performed the ESI analysis in both positive and negative ion modes [10]. In this very excellent paper, the authors have systematically investigated the gasphase uranyl-containing ions and they have examined ligand association/exchange and H/D exchange reactions of the species, using FT-ICR mass spectrometry to obtain accurate mass measurements. In this communication, the collision induced dissociation (CID) of the ions [UO 2 (NOϪ is discussed. The ions were generated from respective salts (UO 2 (NO 3 ) 2 , UO 2 (ClO 4 ) 3 , UO 2 (CH 3 COO) 2 ) by laser desorption/ionization (LDI). As described further, the unusual formation of ion UO 4 Ϫ was detected upon decomposition of the ions subjected to CID. ExperimentalThe LDI mass spectra and LDI MS/MS spectra were obtained on a Waters/Micromass (Manchester, UK) Q-TOF Premier mass spectrometer (software MassLynx ver. 4.1; Manchester, UK) fitted with a 200 Hz repetition rate Nd/YAG laser ( ϭ 355 nm, power density 10 7 W/cm 2 ). For MS/MS experiments, argon was used as a collision gas at the flow-rate 0.5 mL/min in the collision cell. Collision energy (CE -the most important parameter for MS/MS experiments) is indicated in each MS/MS spectrum presented further.To prepare the target spots, 1 L of methanol solution containing uranyl salts was used (the concentration was of about 0.1 mol/dm [3]. After a few min at room temperature, the spot was dry and LDI mass spectra could be recorded. If the concentra...

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“…." [24]. We were able to fragment this ion but the only observed decomposition consisted in the loss of oxygen yielding the fragment ion UO 3 Ϫ (U V -containing ion).…”

Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Uomentioning

confidence: 90%

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Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Sokalska

Prussakowska

Hoffmann

et al. 2010

J. Am. Soc. Mass Spectrom.

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“…54 Anionic species, such as U 2 O 7 H − and U 3 O 10 H − , containing hydrogen atoms were also detected in their mass spectrometric data. They noted that the hydrogen atoms were produced from water or hydroxyl groups in their samples.…”

Section: Introductionmentioning

confidence: 96%

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

et al. 2013

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The structures and bonding of gas-phase [(UO2)2(OH)n](4-n) (n = 2-6) complexes have been studied using density functional theory (DFT), MP2, and CCSD(T) methods with particular emphasis on ground state structures featuring cation-cation interactions (CCIs) between the uranyl groups. An interesting trend is observed in the stabilities of members of this series of complexes. The structures of [(UO2)2(OH)2](2+), [(UO2)2(OH)4], and [(UO2)2(OH)6](2-) featuring CCIs are found at higher energies (by 3-27 kcal/mol) in comparison to their conventional μ2-dihydroxo structures. In contrast, the CCI structures of [(UO2)2(OH)3](+) and [(UO2)2(OH)5](-) are respectively degenerate with and lower in energy than the structures with the μ2-dihydroxo format. The origin of this trend lies in the symmetry-based need to balance the coordination numbers and effective atomic charges of each uranium center. The calculated IR vibrational frequencies provide signature probes that can be used in differentiating the low-energy structures and in experimentally confirming the existence of the structures featuring CCIs.

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Molecular Spectroscopy and Reactions of Actinides in the Gas Phase and Cryogenic Matrices

Gibson¹,

Marçalo²

2010

The Chemistry of the Actinide and Transactinide Elements

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Molecular Uranates: Laser Synthesis of Uranium Oxide Anions in the Gas Phase

Abstract: Laser desorption/ionization of solid uranium trioxide or ammonium diuranate yielded in the gas phase molecular uranium oxide anions with compositions ranging from [ Laser desorption/ionization (LDI), or laser ablation, coupled to mass spectrometry is a technique that has

Cited by 17 publications

References 29 publications

Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes

Molecular Spectroscopy and Reactions of Actinides in the Gas Phase and Cryogenic Matrices

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Molecular Uranates: Laser Synthesis of Uranium Oxide Anions in the Gas Phase

Abstract: Laser desorption/ionization of solid uranium trioxide or ammonium diuranate yielded in the gas phase molecular uranium oxide anions with compositions ranging from [ Laser desorption/ionization (LDI), or laser ablation, coupled to mass spectrometry is a technique that has

Cited by 17 publications

References 29 publications

Unusual ion UO4− formed upon collision induced dissociation of [UO2(NO3)3]−, [UO2(ClO4)3]−, [UO2(CH3COO)3]− ions

Unusual ion UO4− formed upon collision induced dissociation of [UO2(NO3)3]−, [UO2(ClO4)3]−, [UO2(CH3COO)3]− ions

Cation–Cation Interactions in [(UO2)2(OH)n]4–n Complexes

Molecular Spectroscopy and Reactions of Actinides in the Gas Phase and Cryogenic Matrices

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Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Cation–Cation Interactions in [(UO₂)₂(OH)_n]^4–n Complexes