Xe(OTeF5)6, A Deep‐Colored Noble Gas Compound, and OXe(OTeF5)4—The Existence of Kr(OTeF5)2

Lentz, Dieter; Seppelt, Konrad

doi:10.1002/anie.197900661

Cited by 31 publications

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“…The pentafluoroorthotellurate group, OTeF 5 , is comparable to fluorine in its ability to stabilize a variety of noble-gas species. , Derivatives of the OTeF 5 group are known for the 2+, 4+, and 6+ oxidation states of xenon, − as well as for the 2+ oxidation state of krypton . The OTeF 5 analogue of the well-known XeF + cation, XeOTeF 5 + , was first obtained as the AsF 6 - salt by reaction of FXeOTeF 5 with AsF 5 .…”

Section: Introductionmentioning

confidence: 99%

“…The OTeF 5 analogue of the well-known XeF + cation, XeOTeF 5 + , was first obtained as the AsF 6 - salt by reaction of FXeOTeF 5 with AsF 5 . The [XeOTeF 5 ][Sb 2 F 11 ] salt was subsequently synthesized from [XeOTeF 5 ][AsF 6 ] by AsF 5 displacement in liquid SbF 5 . The XeOTeF 5 + cation has been characterized by 19 F, 125 Te, and 129 Xe NMR spectroscopy in SbF 5 solvent 10 and in the solid state by Raman spectroscopy of [XeOTeF 5 ][AsF 6 ] 5,6,9 and [XeOTeF 5 ][Sb 2 F 11 ] .…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2004

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The strong oxidant salt [XeOTeF(5)][Sb(OTeF(5))(6)].SO(2)ClF has been synthesized by reaction of stoichiometric amounts of Xe(OTeF(5))(2) and Sb(OTeF(5))(3) in SO(2)ClF solution at -78 degrees C and characterized in SO(2)ClF solution by low-temperature (17)O, (19)F, (121)Sb, (125)Te, and (129)Xe NMR spectroscopy, showing the Xe...O donor-acceptor bond XeOTeF(5)(+).SO(2)ClF adduct-cation to be labile at temperatures as low as -80 degrees C. The salt crystallizes from SO(2)ClF as [XeOTeF(5)][Sb(OTeF(5))(6)].SO(2)ClF, and the low-temperature crystal structure was obtained: triclinic, P, a = 9.7665(5) A, b = 9.9799(4) A, c = 18.5088(7) A, alpha = 89.293(2) degrees , beta = 82.726(2) degrees , gamma = 87.433(3) degrees , V = 1787.67(13) A(3), Z = 2, and R(1) = 0.0.0451 at -173 degrees C. Unlike MF(6)(-) in [XeF][MF(6)] (e.g., M = As, Sb, Bi) and [XeOTeF(5)][AsF(6)], the Sb(OTeF(5))(6)(-) anion is significantly less basic and does not interact with the coordinately unsaturated xenon(II) cation. Rather, the XeOTeF(5)(+) cation and weak Lewis base, SO(2)ClF, interact by coordination of an oxygen atom of SO(2)ClF to xenon [Xe...O, 2.471(5) A]. The XeOTeF(5)(+).SO(2)ClF adduct-cation has also been studied by low-temperature Raman spectroscopy, providing frequencies that have been assigned to adducted SO(2)ClF. The solid-state Raman spectra of XeOTeF(5)(+).SO(2)ClF and Sb(OTeF(5))(6)(-) have been assigned with the aid of electronic structure calculations. In addition to optimized geometries and vibrational frequencies, theoretical data, including gas-phase donor-acceptor bond energies, natural bond orbital (NBO) analyses, and topological analyses based on electron localization functions (ELF), provide descriptions of the bonding in XeOTeF(5)(+).SO(2)ClF and related systems. The quantum mechanical calculations provided consistent trends for the relative strengths of the Xe...O donor-acceptor bond in XeOTeF(5)(+).SO(2)ClF and ion-pair bonds in [XeL][MF(6)] (L = F, OTeF(5); M = As, Sb), with the Xe...O bond of XeOTeF(5)(+).SO(2)ClF being the weakest in the series.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2004

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Helium Group Compounds

Schrobilgen

Whalen

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Compounds of the helium‐group gases, known since 1962, are limited to those of xenon, krypton, and radon. These heavy noble gases form stable compounds and adducts with fluorine and other powerful oxidants. Xenon has the best studied, most extensive chemistry. The oxidation states observed for xenon range from \documentclass{article}\pagestyle{empty}\begin{document}${+}$\end{document} to \documentclass{article}\pagestyle{empty}\begin{document}${+8}$\end{document} . Bonds to fluorine, oxygen, nitrogen, and carbon have been characterized. The chemistry of krypton, which has one known oxidation state, \documentclass{article}\pagestyle{empty}\begin{document}${+2}$\end{document} , is far less extensive, but bonds to fluorine, oxygen, and nitrogen have been characterized. That of radon is even less well characterized and is limited to fluoride species of the \documentclass{article}\pagestyle{empty}\begin{document}${+2}$\end{document} oxidation state. Properties of the compounds are reviewed.

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Noble‐Gas Compounds

Schrobilgen

Moran

2003

Kirk-Othmer Encyclopedia of Chemical Technology

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Noble‐gas reactivity was discovered in 1962 when Neil Bartlett showed that xenon gas was oxidized by PtF 6 to XePtF 6 . Pursuant to his discovery, numerous xenon and krypton compounds were synthesized in macroscopic quantities. Among the noble‐gas elements, xenon has the most extensive chemistry, and can possess formal oxidation states of 0, +½, +2, +4, +6 and +8 in its compounds by forming fluorides, oxides and oxide fluorides as well as derivatives in which xenon is bonded to polyatomic groups through oxygen, nitrogen and carbon. In addition, several compounds containing Xe‐Au bonds and one compound containing an Xe‐Xe bond are known. Other xenon‐element bonds are known in the gas phase or in low‐temperature matrices, which provide examples of Xe‐H, Xe‐Si, Xe‐S, Xe‐X (X = Cl, Br, I) and Xe‐U bonds. Krypton chemistry is more limited. Only compounds with krypton in the +2 oxidation state are known, namely, KrF 2 , salts of the KrF + and Kr 2 F 3 + cations, by analogy with xenon, Kr(OTeF 5 ) 2 and several species containing Kr‐N bonds. Several gas‐phase and matrix‐isolated species in which krypton is bonded to carbon, hydrogen and halides other than fluorine are also known. Radon is believed to form RnF 2 and RnF + by analogy with krypton and xenon. The only argon species that are known are the ArF + cation, which has been observed in the gas phase, and HArF, which has been stabilized in a low‐temperature argon matrix. To date, no argon, neon or helium compounds have been isolated in macroscopic amounts. Noble‐gas compounds have been utilized as oxidizers and oxidative fluorinating agents in chemical syntheses.

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Xe(OTeF₅)₆, A Deep‐Colored Noble Gas Compound, and OXe(OTeF₅)₄—The Existence of Kr(OTeF₅)₂

Cited by 31 publications

References 14 publications

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

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

Helium Group Compounds

Noble‐Gas Compounds

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Xe(OTeF5)6, A Deep‐Colored Noble Gas Compound, and OXe(OTeF5)4—The Existence of Kr(OTeF5)2

Cited by 31 publications

References 14 publications

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

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

Helium Group Compounds

Noble‐Gas Compounds

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Xe(OTeF₅)₆, A Deep‐Colored Noble Gas Compound, and OXe(OTeF₅)₄—The Existence of Kr(OTeF₅)₂

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

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