Syntheses, infrared and Raman spectra of rare earth(III) fluoroarsenates(V)

Fele‐Beuermann, M.; Lutar, K.; Mazej, Zoran; Milićev, S.; Žemva, Boris

doi:10.1016/s0022-1139(98)00090-6

Cited by 17 publications

(14 citation statements)

References 26 publications

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“…[1] The composition of rare earth() fluoroarsenates() and the fluorine acceptor abilities of AsF 5 suggests formation of a fluorine bridge between the Ln and As atoms (in agreement with the expected shifts in electron density according to ''Gutmann's second rule'' [14] ). Consequently, the distorted octahedral [AsF 6 ] Ϫ ions of maximally C 4v symmetry are anticipated.…”

supporting

confidence: 53%

“…Judging by the results presented in Table 1, the differences between two independent parallel determinations of [AsF 6 ] Ϫ ions seem to increase with increasing fluoroacidity [1,10,11] of the rare-earth trifluorides along the series. The determined amounts of (F Ϫ ) f were abnormally high since binary compounds of the type LnF 3 do not release fluoride ions, as determined in aqueous suspension of the sample directly with a fluoride-ion-selective electrode.…”

Section: Resultsmentioning

confidence: 81%

“…The results of the determination of the [AsF 6 ] Ϫ ion in LnF n (AsF 6 ) 3-n compounds [1] were lower than theoretically calculated values and did not agree with the amount of determined Ln III and (F Ϫ ) t ions [the following abbreviations are used within this paper: (F Ϫ ) t ϭ total fluoride, (F Ϫ ) P ϭ total fluoride in the precipitate, (F Ϫ ) F ϭ free fluoride in the filtrate, (F Ϫ ) f ϭ free fluoride in solution]. Moreover, repetition with several weights of the sample after suspension in water showed that the results were irreproducible.…”

Section: Resultsmentioning

confidence: 99%

“…[1] The results of elemental chemical analyses indicated the presumed composition of the obtained compounds. [1] Crystal structure data are still lacking for these compounds.…”

Section: Introductionmentioning

confidence: 88%

“…The observed number of bands in vibrational spectra of rare earth() fluoroarsenates() support that assumption and indicate a covalent contribution to the bonding between LnF 3 and AsF 5 through fluorine bridges. [1] Molecules undergo whatever distortion necessary to maximize the stability of the entire species (cations ϩ anions). However, that the anion is distorted makes it easier for a positive, protic hydrogen to pull off a fluorine atom from the [AsF 6 ] Ϫ ion (presumably, at least one F has a longer LnϪF bond and so is enroute to dissociation) when suspending these solid compounds in water.…”

mentioning

confidence: 99%

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The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF₆]⁻ Ion

2004

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Results of elemental chemical analyses of the coordination compounds of the type LnFn(AsF6)3‐n (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) indicated unexpectedly low stability of the generally highly hydrolytically stable [AsF6]− ion. Experiments conducted on model compounds of the type NdFn(AsF6)3‐n have shown that hydrolysis proceeded instantaneously during the reaction of the solid compound with water. The ligand substitution catalysis of the compounds is explained in terms of the distortion of the [AsF6]− octahedra earlier shown by vibrational spectroscopy. The study contrasts formally related reactions on the solid−solvent interface as opposed to those in homogeneous solution. A new look at some long studied and well‐known inorganic species is offered. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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supporting

confidence: 53%

Section: Resultsmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 99%

“…[1] The results of elemental chemical analyses indicated the presumed composition of the obtained compounds. [1] Crystal structure data are still lacking for these compounds.…”

Section: Introductionmentioning

confidence: 88%

mentioning

confidence: 99%

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The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF₆]⁻ Ion

2004

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ChemInform Abstract: Syntheses, Infrared and Raman Spectra of Rare Earth(III) Fluoroarsenates(V).

et al. 1998

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XeF₂ Coordination to La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Y in Rare‐Earth Metal(III) Tetrafluoridoborates

Mazej

Goreshnik

2021

Eur J Inorg Chem

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Removal of volatiles at 243 K from solutions of completely dissolved LnF 3 (Ln = La-Dy and Y) and XeF 2 (molar ratio 1 : 3) in anhydrous HF acidified with an excess of BF 3 resulted in [Ln(XeF 2 ) 3 ](BF 4 ) 3 salts. Isolated solids are stable at 298 K and give similar Raman spectra. [La(XeF 2 ) 3 ](BF 4 ) 3 crystallizes in the monoclinic space group C2/m at 150 K. Each La atom is coordinated with three XeF 2 ligands. Six F atoms provided by six bridging BF 4 units, that connect the neighboring La 3 + atoms into columns, complete the nine-fold coordination of each La atom. Chemical reactions carried out in the same way but with molar ratio LnF 3 : XeF 2 = 1 : 1 yielded [Ln(XeF 2 )](BF 4 ) 3 salts (La -Nd). Crystal structures of La and Nd salts are isotypic and crystallize in the monoclinic space group P2 1 /m at 150 K (La) and 200 K (Nd). Each Ln center is coordinated by nine fluorine atoms provided by eight BF 4 units and one XeF 2 ligand. The BF 4 groups interconnect the Ln atoms into two-dimensional layers. With molar ratio LnF 3 : XeF 2 = 1 : 2 and the same synthetic approach, only La yielded [La(XeF 2 ) 2 ](BF 4 ) 3 salt. Prolonged pumping of [Ln(XeF 2 ) n ](BF 4 ) 3 (n = 3, 2, 1) at 298 K or attempts of the isolation at 298 K resulted in products with lower content of XeF 2 or in mixtures of various products. In addition to [Ln-(XeF 2 )](BF 4 ) 3 and LnF 3 /BF 3 products, the [Ln(XeF 2 )]F(BF 4 ) 2 salts (Ln = La, Nd, Sm, Eu, Tb, Dy and Y) also formed. The crystal structures of LaF(HF)(BF 4 ) 2 and LaF(BF 4 ) 2 side products were determined.

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Syntheses, infrared and Raman spectra of rare earth(III) fluoroarsenates(V)

Cited by 17 publications

References 26 publications

The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF₆]⁻ Ion

The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF₆]⁻ Ion

ChemInform Abstract: Syntheses, Infrared and Raman Spectra of Rare Earth(III) Fluoroarsenates(V).

XeF₂ Coordination to La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Y in Rare‐Earth Metal(III) Tetrafluoridoborates

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Syntheses, infrared and Raman spectra of rare earth(III) fluoroarsenates(V)

Cited by 17 publications

References 26 publications

The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF6]− Ion

The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF6]− Ion

ChemInform Abstract: Syntheses, Infrared and Raman Spectra of Rare Earth(III) Fluoroarsenates(V).

XeF2 Coordination to La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Y in Rare‐Earth Metal(III) Tetrafluoridoborates

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Product

Resources

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The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF₆]⁻ Ion

The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF₆]⁻ Ion

XeF₂ Coordination to La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Y in Rare‐Earth Metal(III) Tetrafluoridoborates