Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF5][Sb(OTeF5)6]·SO2ClF

Mercier, Hélène P. A.; Moran, Matthew D.; Sanders, Jeremy C. P.; Schrobilgen, Gary J.; Suontamo, Reijo

doi:10.1021/ic0400890

Cited by 32 publications

(32 citation statements)

References 55 publications

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“…The toroidal shapes of their Ng valence basins (Figure 5) result from the combination of the three valence electron lone pair domains of Ng, with the atomic core electron basin (C(Ng)) lying at the center of the torus. Similar toroidal valence basins have been noted for the Ng (Ng=Kr or Xe) atoms of XeF 2 , [26] [XeF 3 ] − , [26] [XeOTeF 5 ][Sb(OTeF 5 ) 6 ]⋅SO 2 ClF, [27] F 4 OCrFNgF, F 4 OCrFNgFCrOF 4 , [28] and [F 5 Xe(FKrF) n AsF 6 ] ( n =1, 2) [11] . The small perturbations of the V(Ng) toroidal basins of 1′ , 2′ , and 3′ arise from accommodation of the V(Ng) basins to the asymmetries of their immediate environments [11, 28] …”

Section: Resultssupporting

confidence: 70%

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKr^IIFXe^IIF][AsF₆]⋅0.5 Kr^IIF₂⋅2 HF, ([Kr^II₂F₃][AsF₆])₂⋅Xe^IVF₄, and Xe^IVF₄⋅Kr^IIF₂

et al. 2021

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Reaction of [XeF][AsF6] with excess KrF2 at −78 °C in anhydrous HF (aHF) solvent has yielded the first mixed KrII/XeII noble‐gas compound, [FKrFXeF][AsF6] ⋅0.5 KrF2⋅2 HF, a salt of the [FKrFXeF]+ cation. The potent oxidative fluorinating properties of KrII fluoride species resulted in oxidation of XeII to XeIV in aHF at −60 °C to form the mixed KrII/XeIV cocrystals, ([Kr2F3][AsF6])2⋅XeF4 and XeF4⋅KrF2. Further decomposition at 22 °C resulted in oxidation of XeIV to XeVI to give the recently reported KrII/XeVI complexes, [F5Xe(FKrF)n][AsF6] (n=1, 2), [F5Xe][AsF6], and a new KrII/XeVI complex, [(F5Xe)2(μ‐FKrF)(AsF6)2], which was characterized by low‐temperature (LT) Raman spectroscopy. The [FKrFXeF][AsF6]⋅0.5 KrF2⋅2 HF, ([Kr2F3][AsF6])2⋅XeF4 , and XeF4⋅KrF2 compounds were characterized by LT Raman spectroscopy and single‐crystal X‐ray diffraction. Quantum‐chemical calculations were used to assess the bonding in [FKrFXeF]+, [Kr2F3]+, and [Xe2F3]+ and to aid in their vibrational assignments.

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Section: Resultssupporting

confidence: 70%

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKr^IIFXe^IIF][AsF₆]⋅0.5 Kr^IIF₂⋅2 HF, ([Kr^II₂F₃][AsF₆])₂⋅Xe^IVF₄, and Xe^IVF₄⋅Kr^IIF₂

et al. 2021

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“…In addition to [B(OTeF 5 ) 4 ] À [77,78] anumber of hexacoordinate [M(OTeF 5 ) 6 ] nÀ ions (where n = 1; M = Sb, [79,80] As, [80,81] Bi, [80] Nb, [79,82] ; n = 2, M = Ti [83] )h ave also been investigated. Themost commonly used anion of this group is the antimonybased [Sb(OTeF 5 ) 6 ] À ion, which is able to stabilize reactive or weakly bound complex cations,f or example,[ XeOTeF 5 ] + , [84] [Ag(S 8 ) 2 ] + , [85] and [Ag 2 (Se 6 )(SO 2 ) 2 ] + . [86] Very recently the aluminum analogue [Al(OTeF 5 ) 4 ] À was reported as as eries of salts with the synthetically useful cations Cs + and [Ph 3 C] + .…”

Section: Teflate-based Anionsmentioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

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“…Recently, the group of pentafluoroorthotellurate (teflate) based WCAs which are considered to be highly oxidation resistant, was expanded by the successful synthesis and characterization of the novel anion [Al(OTeF 5 ) 4 ] – . Its facile one‐pot synthesis combined with its weak coordinating and chemical robust properties renders this WCA to be a promising candidate for the synthesis of novel unstable, cationic species.…”

Section: Introductionmentioning

confidence: 99%

Salts of the Weakly Coordinating Anion [Al(OTeF₅)₄]^– containing Reactive Counterions

Hoffmann¹,

Wiesner²,

Subat³

et al. 2018

Zeitschrift anorg allge chemie

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Six different salts of the weakly coordinating anion [Al(OTeF5)4]– were synthesized and characterized spectroscopically. The alkali and silver salts M[Al(OTeF5)4] (M = Ag, Li, Na, K, Rb) were obtained by a protonation reaction involving the Brønsted acid H[Al(OTeF5)4](solv). In the case of the lithium and silver salt, crystals of the solvent‐coordinated [Li(thf)4][Al(OTeF5)4(thf)2] and [Ag(thf)6][Al(OTeF5)4(thf)2] were characterized by low‐temperature X‐ray diffraction, revealing a sixfold coordinated central aluminum atom. By a metathesis reaction, the oxidizing nitrosonium salt [NO][Al(OTeF5)4] was obtained and its reactivity was demonstrated by a reaction with white phosphorus. By low‐temperature NMR spectroscopy the selective formation of [NOP4]+ species was confirmed. All of the prepared salts represent useful starting materials for the further introduction of the weakly coordinating anion [Al(OTeF5)4]– into a given system.

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Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

Cited by 32 publications

References 55 publications

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKr^IIFXe^IIF][AsF₆]⋅0.5 Kr^IIF₂⋅2 HF, ([Kr^II₂F₃][AsF₆])₂⋅Xe^IVF₄, and Xe^IVF₄⋅Kr^IIF₂

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKr^IIFXe^IIF][AsF₆]⋅0.5 Kr^IIF₂⋅2 HF, ([Kr^II₂F₃][AsF₆])₂⋅Xe^IVF₄, and Xe^IVF₄⋅Kr^IIF₂

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Salts of the Weakly Coordinating Anion [Al(OTeF₅)₄]^– containing Reactive Counterions

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Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF5][Sb(OTeF5)6]·SO2ClF

Cited by 32 publications

References 55 publications

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKrIIFXeIIF][AsF6]⋅0.5 KrIIF2⋅2 HF, ([KrII2F3][AsF6])2⋅XeIVF4, and XeIVF4⋅KrIIF2

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKrIIFXeIIF][AsF6]⋅0.5 KrIIF2⋅2 HF, ([KrII2F3][AsF6])2⋅XeIVF4, and XeIVF4⋅KrIIF2

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Salts of the Weakly Coordinating Anion [Al(OTeF5)4]– containing Reactive Counterions

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Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKr^IIFXe^IIF][AsF₆]⋅0.5 Kr^IIF₂⋅2 HF, ([Kr^II₂F₃][AsF₆])₂⋅Xe^IVF₄, and Xe^IVF₄⋅Kr^IIF₂

Syntheses and Characterizations of the Mixed Noble‐Gas Compounds, [FKr^IIFXe^IIF][AsF₆]⋅0.5 Kr^IIF₂⋅2 HF, ([Kr^II₂F₃][AsF₆])₂⋅Xe^IVF₄, and Xe^IVF₄⋅Kr^IIF₂

Salts of the Weakly Coordinating Anion [Al(OTeF₅)₄]^– containing Reactive Counterions