Generation of gas‐phase zirconium fluoroanions by electrospray of an ionic liquid

Groenewold, Gary S.; Delmore, J.E.; Benson, Michael; Tsuda, Tetsuya; Hagiwara, Rika

doi:10.1002/rcm.6890

Cited by 3 publications

(14 citation statements)

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“…Density functional theory [62] calculations were performed at the B3LYP level of theory [63,64], with the 6-311++G(d,p) basis set for all atoms. Calculations were initiated starting from a variety of structures that were generated by intuition and previous experience with similar zirconium-ionic liquid complexes [60]. All calculated structures are true minima (i.e., no imaginary frequencies).…”

Section: Methodsmentioning

confidence: 99%

“…Facile ESI production of IL-derived ion pairs was used to measure relative anion-cation binding energies by collision induced dissociation reactions that displayed trends similar to those generated using density functional theory (DFT) calculations [58]. -was originally developed by Hagiwara and coworkers [13-18, 20, 22, 24, 25] with the objective of generating a fluorinating environment for organic fluorination reactions [26][27][28] - [60]. The Zr fluoroanions were observed by diluting the IL-Zr solutions in acetonitrile and electrospraying the resulting solutions.…”

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confidence: 99%

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Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Zarzana

Groenewold

Benson

et al. 2015

J. Am. Soc. Mass Spectrom.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Zarzana

Groenewold

Benson

et al. 2015

J. Am. Soc. Mass Spectrom.

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“…The mass spectra in positive and negative modes contain base signals at m/z 99 and 77, corresponding to [ZrO(H 2 O) 5 ] 2 + and [ZrO 2 (OH) 2 ] 2À , respectively. The cluster ion [17] at m/z 115. For concentrations > 10 À 4 mol L À 1 , Zr(IV) shows a strong tendency to hydrolysis and polymerization, even at low pHs.…”

Section: Zr(iv) Ions Assignmentsmentioning

confidence: 99%

“…[17] Metal fluorides have a high electronic affinity, resulting in the formation of predominant species compared to oxyanions. [17,22] Besides, they can provide isotopic envelopes that suffer little or no interference from other electronegative elements. [17]…”

Section: Zr(iv) Ions Assignmentsmentioning

confidence: 99%

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Unveiling the Zirconium and Hafnium Speciation in Fluoride‐Nitric Acid Solutions by Paper Spray Ionization Mass Spectrometry Combined with DFT Calculations

et al. 2021

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Paper spray ionization mass spectrometry (PSI-MS) was used to detect a variety of species of hafnium and zirconium present in an aqueous acid solution containing NO 3 À and F À anions. This solution mimetics the acid waters used in separation/extraction processes. Hence, the information provided by PSI-MS is combined with the results achieved from DFT calculations to confirm the nature and stability of each species. In the adopted experimental conditions, Zr(IV) appears coordinated with F À , NO 3 À and H 2 O to generate mainly the dimer [Zr 2 F 3 OH-(NO 3) 2 (H 2 O) 5 ] 2 + , among other complexes, with remarkable thermodynamic stability (À 48.7 kcal mol À 1). On the other hand, Hf(IV) emerges predominantly coordinated with NO 3 À and F À anions. The hafnium monomers [HfF 4 NO 3 ] À and [HfF 3 (NO 3) 2 ] À have thermodynamic stability related to the electron pairing of the valence layer. In the gas phase, the fluoroanions of Zr(IV) demonstrated a high electronic affinity and free energy via DFT (À 156.7 kcal mol À 1) correlating thermodynamic stability to the experimental (À 47 kcal mol À 1), for the formation reaction of [ZrF 5 ] À. Besides, the presence of fluoride and nitrate in the reaction mixture induces the formation of dimers connected in μ 2-F bridges, with coordination 7 and 8 of the central atom. Finally, the results described herein are promising studies of chemical speciation of cationic metals in an aqueous environment, a challenging subject whose importance will grow in the coming years.

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Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]⁺[F(HF)_2.3]⁻ Ionic Liquid

Zarzana

Groenewold

Benson

et al. 2018

J. Am. Soc. Mass Spectrom.

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A new methodology for gas-phase uranium ion formation is described in which UO is dissolved in neat N-ethyl,N'-methylimidazolium fluorohydrogenate ionic liquid [EMIm][F(HF)], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF (a U(V) species) was observed at m/z = 352, and other than cluster ions derived from the ionic liquid, nothing else was observed. When the sample was analyzed using infusion desorption chemical ionization, UF was the base peak, and it was accompanied by a less intense UF that most likely was formed by elimination of a fluorine radical from UF. Formation of UF required dissolution of UO followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Dissolution of UO produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF provides a vehicle for accurate measurement of uranium isotopic abundances free from interference from minor isotopes of other elements and a convenient ion synthesis route that is needed gas-phase structure and reactivity studies like infrared multiphoton dissociation and ion-molecule dissociation and condensation reactions. The reactive fluorohydrogenate ionic liquid may also enable conversion of uranium in oxidic matrices into uranium fluorides that slowly oxidize to uranyl fluoride under ambient conditions, liberating the metal for facile measurement of isotope ratios without extensive chemical separations. Graphical abstract ᅟ.

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Generation of gas‐phase zirconium fluoroanions by electrospray of an ionic liquid

Cited by 3 publications

References 24 publications

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Unveiling the Zirconium and Hafnium Speciation in Fluoride‐Nitric Acid Solutions by Paper Spray Ionization Mass Spectrometry Combined with DFT Calculations

Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]⁺[F(HF)_2.3]⁻ Ionic Liquid

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Generation of gas‐phase zirconium fluoroanions by electrospray of an ionic liquid

Cited by 3 publications

References 24 publications

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid

Unveiling the Zirconium and Hafnium Speciation in Fluoride‐Nitric Acid Solutions by Paper Spray Ionization Mass Spectrometry Combined with DFT Calculations

Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]+[F(HF)2.3]− Ionic Liquid

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Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]⁺[F(HF)_2.3]⁻ Ionic Liquid