The solution thermochemistry of antimony pentafluoride and some fluoroantimonates

Burgess, John; Peacock, R. D.; Sherry, Robert

doi:10.1016/s0022-1139(00)82279-4

Cited by 12 publications

(8 citation statements)

References 20 publications

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“…Although a value for Δ f H o (SbF 5 , g) = -1301 kJ mol -1 has been established, 80 there is no value in the literature for Δ f G o (SbF 5 , g). However, Δ f G o (SbF 5 , l) = -1242 kJ mol -1 has been reported.…”

Section: Resultsmentioning

confidence: 99%

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

et al. 2010

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The crystal structures of the xenon(II) salts, [XeF][SbF(6)], [XeF][BiF(6)], and [XeF][Bi(2)F(11)], have been determined for the first time, and those of XeF(2), [XeF][AsF(6)], [XeF][Sb(2)F(11)], and [XeF(3)][Sb(2)F(11)] have been redetermined with greater precision at -173 °C. The Bi(2)F(11)(-) anion, which has a structure analogous to those of the As(2)F(11)(-) and Sb(2)F(11)(-) anions, has been structurally characterized by single crystal X-ray diffraction for the first time as its XeF(+) salt. The fluorine bridge between the bismuth atoms is asymmetric with Bi---F(b) bond lengths of 2.092(6) and 2.195(6) A and a Bi---F(b)'---Bi bridge bond angle of 145.3(3)°. The XeF(+) cations interact with their anions by means of Xe---F(b)---M bridges. Consequently, the solid-state Raman spectra of [XeF][MF(6)] (M = As, Sb, Bi) were modeled as the gas-phase ion pairs and assigned with the aid of quantum-chemical calculations. Relationships among the terminal Xe-F(t) and bridge Xe---F(b) bond lengths and stretching frequencies and the gas-phase fluoride ion affinities of the parent Lewis acid that the anion is derived from are considered. The analogous krypton ion pairs, [KrF][MF(6)] (M = As, Sb, Bi) were also calculated and compared with their previously published X-ray crystal structures. The calculated cation-anion charge separations indicate that the [XeF][MF(6)] salts are more ionic than their krypton analogues and that XeF(2) is a stronger fluoride ion donor than KrF(2). The lattice energies, standard enthalpies, and free energies of formation for salts containing the NgF(+), Ng(2)F(3)(+), XeF(3)(+), XeF(5)(+), Xe(2)F(11)(+), and XeOF(3)(+) (Ng = Ar, Kr, Xe) cations were estimated using volume-based thermodynamics (VBT) based on crystallographic and estimated ion volumes. These estimated parameters were then used to predict the stabilities of noble-gas salts. VBT is used to examine and predict the stabilities of, inter alia, the salts [XeF(m)][Sb(n)F(5n+1)] and [XeF(m)][As(n)F(5n+1)] (m = 1, 3; n = 1, 2). VBT also confirms that XeF(+) salts are stable toward redox decomposition to Ng, F(2), and MF(5) (M = As, Sb), whereas the isolable krypton compounds and the unknown ArF(+) salts are predicted to be unstable by VBT with the ArF(+) salts being the least stable.

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Section: Resultsmentioning

confidence: 99%

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

et al. 2010

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“…The enthalpies of formation of a collection of [SbF 6 ] À salts were discussed in Refs. [48,51] studies that included the alkali metals and O 2 + . Since the lattice energy of NO + -salts and Cs + salts have been equated [52] we can now posit almost thermoneutrality (i.e.…”

Section: Synthesesmentioning

confidence: 99%

Nitrosyl and dioxygenyl cations and their salts—Similar but further investigation needed

Mazej

Ponikvar‐Svet

Liebman

et al. 2009

Journal of Fluorine Chemistry

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“…The reaction enthalpy of this interaction, i.e., the fluoride ion affinity, serves as a good measure for the strength of a Lewis acid. Since only a small number of fluoride ion affinities had been estimated experimentally and often with relatively large uncertainties and discrepancies due to the use of different techniques [3][4][5][6][7][8][9][10], it was important to create a selfconsistent set of fluoride ion affinities containing essentially all of the important Lewis acids.…”

Section: Quantitative Scale For Lewis Aciditymentioning

confidence: 99%

On a quantitative scale for Lewis acidity and recent progress in polynitrogen chemistry

Christe

Dixon

McLemore

et al. 2000

Journal of Fluorine Chemistry

402

328

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The solution thermochemistry of antimony pentafluoride and some fluoroantimonates

Cited by 12 publications

References 20 publications

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

Nitrosyl and dioxygenyl cations and their salts—Similar but further investigation needed

On a quantitative scale for Lewis acidity and recent progress in polynitrogen chemistry

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The solution thermochemistry of antimony pentafluoride and some fluoroantimonates

Cited by 12 publications

References 20 publications

X-ray Crystal Structures of [XeF][MF6] (M = As, Sb, Bi), [XeF][M2F11] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

X-ray Crystal Structures of [XeF][MF6] (M = As, Sb, Bi), [XeF][M2F11] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

Nitrosyl and dioxygenyl cations and their salts—Similar but further investigation needed

On a quantitative scale for Lewis acidity and recent progress in polynitrogen chemistry

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Product

Resources

About

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics

X-ray Crystal Structures of [XeF][MF₆] (M = As, Sb, Bi), [XeF][M₂F₁₁] (M = Sb, Bi) and Estimated Thermochemical Data and Predicted Stabilities for Noble-Gas Fluorocation Salts using Volume-Based Thermodynamics