Molecular Structure of Xenon Tetroxide, XeO4

Gundersen, Grete; Hedberg, Kenneth; Huston, John L.

doi:10.1063/1.1673060

Cited by 41 publications

(22 citation statements)

References 15 publications

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“…The differences between calculated frequencies and experimental values for the 18 O‐enriched compounds remain essentially constant over the series of Xe 16/18 O 4 isotopomers. Overall, the absolute values of the 16/18 O isotopic shifts of XeO 4 are greater than those of [XeO 6 ] 4− (Table 3), in accordance with the relative bond strengths and XeO bond lengths of XeO 4 (1.736(2) Å)5 and [XeO 6 ] 4− in NaXeO 6 ⋅ 8 H 2 O (1.864(12) Å) 18…”

Section: Resultssupporting

confidence: 74%

“…Xenon trioxide and XeO 4 decompose explosively to their elements with the release of 4021 and 642 kJ mol −1 ,2 respectively, whereas water‐insoluble XeO 2 decomposes at 0 °C over several minutes to Xe and O 2 3. Despite their hazardous natures, the molecular structures of XeO 3 and XeO 4 have been obtained from a single‐crystal X‐ray diffraction study on XeO 3 4 and an electron diffraction study on gaseous XeO 4 5. Vibrational frequencies for XeO 4 have been previously obtained by gas‐phase IR spectroscopy6 and by Raman spectroscopy in the solid state7 and in anhydrous HF 8…”

Section: Introductionmentioning

confidence: 99%

“…The shock‐sensitive and treacherous nature of XeO 4 has no doubt impeded progress in Xe VIII chemistry, which has progressed little beyond the synthesis and structural characterization of the remarkably stable perxenate anion, [XeO 6 ] 4− ,16–19 and the work by Huston and co‐workers,6, 20 who first synthesized and structurally characterized XeO 4 5–7. Huston and co‐workers21 also demonstrated the existence of the only other Xe VIII compounds that are presently known, namely, XeO 3 F 2 , which was characterized by matrix‐isolation IR and Raman spectroscopy, and XeO 2 F 4 ,22 which has only been characterized in the gas phase by mass spectrometry.…”

Section: Introductionmentioning

confidence: 99%

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Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Vent‐Schmidt

Goettel

Schrobilgen

et al. 2015

Chemistry A European J

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The photolytic behavior of the thermochemically unstable xenon(VIII) oxide XeO4 was investigated by UV irradiation in noble-gas and F2 matrices. Photolysis of Xe(16) O4 or Xe(18) O4 in noble-gas matrices at 365 nm yielded XeO3 and a new xenon(VIII) oxide, namely, (η(2) -O2 )XeO3 , which, along with XeO4 , was characterized by matrix-isolation IR spectroscopy and quantum-chemical calculations. Calculations of the UV spectrum showed that the photodecomposition is induced by an n→σ* transition, but the nature of the excitation differs when different light sources are used. There is strong evidence for the formation of mobile (1) D excited O atoms in the case of excitation at 365 nm, which led to the formation of (η(2) -O2 )XeO3 by reaction with XeO4 . Matrix-isolation IR spectroscopy in Ne and Ar matrices afforded the natural-abundance xenon isotopic pattern for the ν3 (T2 ) stretching mode of Xe(16) O4 , and (18) O enrichment provided the (16) O/(18) O isotopic shifts of XeO4 and (η(2) -O2 )XeO3 .

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Section: Resultssupporting

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Vent‐Schmidt

Goettel

Schrobilgen

et al. 2015

Chemistry A European J

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“…Note added in proof: -The structure of XeO4 has now been reported in full by Gundersen, Hedberg & Huston (1970). Huston & Claasen (1970) have shown the similarity of the force constants in IO~-and XeO4, and have contrasted their values of F, the principal nonbonded repulsion constant, with that in OSO4.…”

Section: Discussionmentioning

confidence: 99%

Refinement of the structure of NaIO₄

Kàlmán¹,

Cruickshank²

1970

Acta Crystallogr Sect B

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NaIO4 has been re-examined. It crystallizes in space group 141/a with a = b = 5"337, c = 11.947 A; Z= 4.Anisotropic refinement reduced R to 8"94% for 740 observed reflexions. The vibrationally corrected I-O length is 1"775 + 7 A.. The structure consists of IOn-anions, slightly compressed in the c direction, and Na + cations, each surrounded by eight oxygen atoms at distances of 2.54 or 2"60/~. In~oducfionSodium periodate together with other periodates e.g. KIO4 (Hylleraas, 1926), crystallizes with the lattice type of scheelite (CaWO4) (Hiorthdahl, 1887). The lattice parameters and the space group C~h-I4Ja were determined by Kirkpatrick & Dickinson (1926) who assigned the iodine and sodium atoms to the two fourfold positions (4a and 4b). The oxygen atom parameters were later determined approximately by Hazlewood (1938).The present reinvestigation was undertaken to provide the more precise dimensions now needed for discussions of the bonding in tetrahedral oxyanions. ExperimentalTetragonal bipyramidal crystals of NaIO4 were obtained from an aqueous solution of a Hopkins & Williams Ltd. product, held slightly above 40 ° C. A small well-developed crystal was placed in a drop of distilled water and was rotated in the water by a fine needle slowly but continuously. The progress of the etching of the surface was observed through a binocular stereomicroscope. In this way a small almost spherical specimen was prepared with an average diameter of 0.1 mm. The specimen was then mounted at random on a special goniometer head (K~ilm~in, 1967) by means of which one of the a axes was properly oriented. Equiinclination multiple-film photographs were taken with Mo K~ radiation for the layers: hOl-->h4l. The intensifies were estimated visually using standard scales, made from one good reflexion on each layer. After the data reduction 927 independentt IFol values were obtained, of which 187 were too weak for observation, mainly due to the absence of the iodine and sodium contributions from hkl reflexions with 2k + l= 2n + 2.Owing to the small diameter of the specimen (/zR= 0.47) RefinementFollowing Hazlewood (1938), the space group representation with the iodine atom at the origin at 4 was used. His oxygen parameters were taken as the starting point for a full-matrix least-squares refinement with a program written by Dr J. S. Stephens for the ATLAS computer. Five independent scale factors were used and all atoms were treated with anisotropic vibrations. In order to correct for anomalous dispersion, complex scattering factors were used for iodine [Af'=-0.64, Af"=2.15, Cromer (1965)]. Form factors for neutral atoms were taken from a recent table supplied by Ibers (1968). The final weighting scheme was w--(7.0 + 0.151Fol + 0"008lFol2) -a .The refinement reduced the unweighted residual R to 8. 94% and R'=[~wAZ)/(~w[kFol2)]l/z to 11.60% for the 740 observed reflexions. The final parameters are shown in Table 1 and the structure factors in Table 2.

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“…Xenon tetroxide is prepared by the interaction of concentrated H 2 SO 4 with sodium or barium perxenate, Na 4 XeO 6 , Ba 2 XeO 6 (50,68). The XeO 3 molecule has a trigonal pyramidal shape with a Xe-O bond length of 176(3) pm (69), whereas XeO 4 has a tetrahedral shape with a Xe-O bond of 173.6(2) pm (70). Xenon tetroxide has also been characterized in solution by low temperature 17 O, 129 Xe, and 131 Xe nuclear magnetic resonance (NMR) spectroscopy (68).…”

Section: Introductionmentioning

confidence: 99%

Noble‐Gas Compounds

Schrobilgen

Brock

Mercier

2012

Kirk-Othmer Encyclopedia of Chemical Technology

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Noble‐gas reactivity was discovered on March 23, 1962 when Neil Bartlett (1932–2008) showed that xenon gas was oxidized by PtF 6 . The product obtained by Bartlett was initially formulated as 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 it can possess formal oxidation states of 0, +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, compounds containing Xe–Au, Xe–Xe, Xe–Cl, and Hg–Xe bonds are known. Other xenon‐element bonds are known in the gas phase or in low‐temperature matrices, which are exemplified by 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, the Kr–O bonded compound, 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 used as oxidizers and as oxidative fluorinating agents in chemical syntheses.

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Molecular Structure of Xenon Tetroxide, XeO4

Cited by 41 publications

References 15 publications

Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Refinement of the structure of NaIO₄

Noble‐Gas Compounds

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Molecular Structure of Xenon Tetroxide, XeO4

Cited by 41 publications

References 15 publications

Ultraviolet Photolysis Studies on XeO4 in Noble‐Gas and F2 Matrices and the Formation and Characterization of a New XeVIII Oxide, (η2‐O2)XeO3

Ultraviolet Photolysis Studies on XeO4 in Noble‐Gas and F2 Matrices and the Formation and Characterization of a New XeVIII Oxide, (η2‐O2)XeO3

Refinement of the structure of NaIO4

Noble‐Gas Compounds

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Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Ultraviolet Photolysis Studies on XeO₄ in Noble‐Gas and F₂ Matrices and the Formation and Characterization of a New Xe^VIII Oxide, (η²‐O₂)XeO₃

Refinement of the structure of NaIO₄