Synthesis and characterization by Raman spectroscopy of AsBr<sub>4</sub>AsF<sub>6</sub>; its thermodynamic and kinetic stability and that of related salts

Klapötke, Thomas M.; Passmore, Jack

doi:10.1039/dt9900003815

Cited by 9 publications

(9 citation statements)

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“…Although the nonmetals of the fourth row of the periodic table are unstable in their highest oxidation state, , the entire series of tetrahaloarsonium(V) cations, AsF 4 + , AsCl 4 + , − AsBr 4 + , and AsI 4 + , are now known as well as their tetrahalophosphonium(V) analogs, − NF 4 + , and NCl 4 + . The only tetrahalostibonium(V) cation reported and characterized to date is the SbCl 4 + cation, − and no example of a bismuth analog is presently known.…”

Section: Introductionmentioning

confidence: 99%

“…The tetrahaloarsonium(V) cations have been synthesized as the AsF 4 + PtF 6 - , AsCl 4 + AsF 6 - , − AsBr 4 + AsF 6 - , AsBr 4 + AlBr 4 - /Al 2 Br 7 - , and AsI 4 + AlCl 4 - 8 salts. The AsBr 4 + and AsI 4 + salts are thermodynamically and kinetically unstable, decomposing at −78 °C, whereas AsF 4 + PtF 6 - and AsCl 4 + AsF 6 - are thermodynamically stable.…”

Section: Introductionmentioning

confidence: 99%

“…The AsBr 4 + and AsI 4 + salts are thermodynamically and kinetically unstable, decomposing at −78 °C, whereas AsF 4 + PtF 6 - and AsCl 4 + AsF 6 - are thermodynamically stable. The AsBr 4 + and AsI 4 + salts have been characterized at low temperature by solid state Raman spectroscopy, and their relative stabilities have been rationalized on the basis of simple Born−Haber cycles. , Possible decomposition mechanisms have been proposed, in particular for the AsBr 4 + AsF 6 - salt. The initiating step likely involves fluoride ion transfer from the anion to the cation.…”

Section: Introductionmentioning

confidence: 99%

“…Although PI 4 + AlI 4 - is thermodynamically stable and has been characterized by X-ray crystallography, the recently synthesized salts, PI 4 + AsF 6 - and PI 4 + SbF 6 - , are thermodynamically and kinetically unstable and likely decompose in a manner similar to AsBr 4 + AsF 6 - , since the AsF 6 - salt yields the corresponding products AsF 3 , PF 3 , and I 2 . Interestingly, the salt PBr 4 + PF 6 - was estimated to be only marginally stable with respect to decomposition to PF 5 , PBr 3 , and Br 2 , but it is found to be stable up to 135 °C . Moreover, this salt reacts only slowly with AsF 3 , whereas PCl 4 + PF 6 - is readily converted into PF 5 and AsCl 3 , indicating a marked degree of kinetic stabilization.…”

Section: Introductionmentioning

confidence: 99%

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Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

et al. 1996

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The stable salts, SbCl(4)(+)Sb(OTeF(5))(6)(-) and SbBr(4)(+)Sb(OTeF(5))(6)(-), have been prepared by oxidation of Sb(OTeF(5))(3) with Cl(2) and Br(2), respectively. The SbBr(4)(+) cation is reported for the first time and is only the second example of a tetrahalostibonium(V) cation. The SbCl(4)(+) cation had been previously characterized as the Sb(2)F(11)(-), Sb(2)Cl(2)F(9)(-), and Sb(2)Cl(0.5)F(10.5)(-) salts. Both Sb(OTeF(5))(6)(-) salts have been characterized in the solid state by low-temperature Raman spectroscopy and X-ray crystallography. Owing to the weakly coordinating nature of the Sb(OTeF(5))(6)(-) anion, both salts are readily soluble in SO(2)ClF and have been characterized in solution by (121)Sb, (123)Sb, and (19)F NMR spectroscopy. The tetrahedral environments around the Sb atoms of the cations result in low electric field gradients at the quadrupolar (121)Sb and (123)Sb nuclei and correspondingly long relaxation times, allowing the first solution NMR characterization of a tetrahalocation of the heavy pnicogens. The following crystal structures are reported: SbCl(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.022(1) Å, c = 18.995(4) Å, V = 1652.3(6) Å(3), D(calc) = 3.652 g cm(-)(3), Z = 2, R(1) = 0.0461; SbBr(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.206(1) Å, c = 19.297(3) Å, V = 1740.9(5) Å(3), D(calc) = 3.806 g cm(-)(3), Z = 2, R(1) = 0.0425. The crystal structures of both Sb(OTeF(5))(6)(-) salts are similar and reveal considerably weaker interactions between anion and cation than in previously known SbCl(4)(+) salts. Both cations are undistorted tetrahedra with bond lengths of 2.221(3) Å for SbCl(4)(+) and 2.385(2) Å for SbBr(4)(+). The Raman spectra are consistent with undistorted SbX(4)(+) tetrahedra and have been assigned under T(d)() point symmetry. Trends within groups 15 and 17 are noted among the general valence force constants of the PI(4)(+), AsF(4)(+), AsBr(4)(+), AsI(4)(+), SbCl(4)(+) and SbBr(4)(+) cations, which have been calculated for the first time, and the previously determined force constants for NF(4)(+), NCl(4)(+), PF(4)(+), PCl(4)(+), PBr(4)(+), and AsCl(4)(+), which have been recalculated for the P and As cations in the present study. The SbCl(4)(+) salt is stable in SO(2)ClF solution, whereas the SbBr(4)(+) salt decomposes slowly in SO(2)ClF at room temperature and rapidly in the presence of Br(-) ion and in CH(3)CN solution at low temperatures. The major products of the decompositions are SbBr(2)(+)Sb(OTeF(5))(6)(-), as an adduct with CH(3)CN in CH(3)CN solvent, and Br(2).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

et al. 1996

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“…[5,6] In fact, the entire series of [PX 4 ] + (X = F, [5] Cl, [7] Br, [8] I [9,10] ) and their arsonium analogues are known. [6,[11][12][13][14][15][16] Conversely, only [NF…”

mentioning

confidence: 99%

Donor‐Stabilised [SbF₄]⁺: SbF₅ as a Fluoride‐Ion Donor

O'Donnell

Turnbull

Wetmore

et al. 2021

Chemistry A European J

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Antimony pentafluoride is a strong Lewis acid and fluoride-ion acceptor that has not previously demonstrated any discreet fluoride-ion donor properties. The first donor-stabilised [SbF 4 ] + cations were prepared from the autoionisation of SbF 5 in the presence of bidentate N-donor ligands 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) as their [SbF 6 ] À salts. The [SbF 4 (NÀ N)][Sb 2 F 11 ] (NÀ N = bipy, phen) salts were synthesised by the addition of one equivalent of SbF 5 •SO 2 to [SbF 4 (NÀ N)][SbF 6 ] in liquid SO 2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF 4 (phen)][SbF 6 ] • 3CH 3 CN and [SbF 4 (phen)][SbF 6 ] • 2SO 2 were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron-pair donation from N to Sb stabilizes [SbF 4 ] + with the SbÀ N bond strength being approximately two thirds of that of the SbÀ F bonds in these cations and the cationic charge being primarily ligand-centred.Antimony pentafluoride, SbF 5 , is one of the strongest F À acceptors currently known, forming highly stable [Sb n F 5n + 1 ] À (n = 1-4) anions. Its solutions in anhydrous HF (aHF) are some of the strongest recorded Bronsted superacids. Antimony pentafluoride is also the benchmark for Lewis superacidity, as molecular Lewis acids with fluoride-ion affinities (FIAs) greater than monomeric SbF 5 in the gas phase (calcd. 501 kJ mol À 1 , exptl. 506 � 60 kJ mol À 1 ) are considered Lewis superacids. [1][2][3] The formation of polynuclear anions, however, can drive the already extreme FIA of SbF 5 even higher. [4] Thus, it is unsurprising that, aside from self-association of solid and liquid SbF 5 to form cis-linked SbF 6 octahedra, the ability of SbF 5 to act as a discrete F À donor is hitherto unknown. However, the lighter pnictogen pentafluorides, PF 5 and AsF 5 , have both previously demonstrated the ability to act as F À donors and form [PnF 4 ] + cations (Pn = P and As). [5,6] In fact, the entire series of [PX 4 ] + (X = F, [5] Cl, [7] Br, [8] I [9,10] ) and their arsonium analogues are known. [6,[11][12][13][14][15][16] Conversely, only [NF

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ChemInform Abstract: Synthesis and Characterization by Raman Spectroscopy of AsBr4AsF6; Its Thermodynamic and Kinetic Stability and that of Related Salts.

Klapoetke

Passmore

1991

ChemInform

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Synthesis and Characterization by Raman Spectroscopy of AsBr4AsF6; Its Thermodynamic and Kinetic Stability and that of Related Salts.-The title compound is prepared by oxidation of AsBr3 and Br2 by AsF5, as outlined in the scheme. Characterization of the thermodynamically and kinetically unstable salt by using Raman spectroscopy at -196 . degree.C shows that its decomposition to AsF3 and Br2 follows a course via AsBr3. Attempts to prepare the more stable AsBr4AlBr4 by reaction of stoichiometric amounts of AsBr3, Br2 and AlBr3 fail. The viscous liquid obtained is shown to be an equilibrium mixture of AsBr4AlBr4 with AsBr3, Br2, and AsBr4Al2Br7. The low stability of AsBr4AsF6, contrasting with that of AsCl4AsF6, is discussed in terms of a simple energetics model. -(KLAPOETKE, T.; PASSMORE, J.; J. Chem. Soc., Dalton Trans. (1990) 12, 3815-3822; Dep. Chem., Univ. New Brunswick, Fredericton, New Brunswick, Can. E3B 6E2; EN)

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Synthesis and characterization by Raman spectroscopy of AsBr₄AsF₆; its thermodynamic and kinetic stability and that of related salts

Cited by 9 publications

References 26 publications

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

Donor‐Stabilised [SbF₄]⁺: SbF₅ as a Fluoride‐Ion Donor

ChemInform Abstract: Synthesis and Characterization by Raman Spectroscopy of AsBr4AsF6; Its Thermodynamic and Kinetic Stability and that of Related Salts.

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Synthesis and characterization by Raman spectroscopy of AsBr4AsF6; its thermodynamic and kinetic stability and that of related salts

Cited by 9 publications

References 26 publications

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and 19F, 121Sb, and 123Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl4+Sb(OTeF5)6- and SbBr4+Sb(OTeF5)6-

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and 19F, 121Sb, and 123Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl4+Sb(OTeF5)6- and SbBr4+Sb(OTeF5)6-

Donor‐Stabilised [SbF4]+: SbF5 as a Fluoride‐Ion Donor

ChemInform Abstract: Synthesis and Characterization by Raman Spectroscopy of AsBr4AsF6; Its Thermodynamic and Kinetic Stability and that of Related Salts.

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Synthesis and characterization by Raman spectroscopy of AsBr₄AsF₆; its thermodynamic and kinetic stability and that of related salts

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

Donor‐Stabilised [SbF₄]⁺: SbF₅ as a Fluoride‐Ion Donor