Xenon Tetroxide: Preparation and Some Properties

Selig, H.; Claassen, Howard H.; Chernick, Cedric L.; Malm, John G.; Huston, John L.

doi:10.1126/science.143.3612.1322

Cited by 67 publications

(33 citation statements)

References 5 publications

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“…Thus the molecular orbital model predicts an octahedral structure for XeF6, whereas the valence bond model anticipates a distorted octahedron, all of the valence shell electrons being sterically active, as in IF,. Some support for this expectation is given by the involvement of all eight valence electrons in xenon trioxide (25), the perxenates (26), and xenon tetroxide (27). I t is interesting to note that if XeF6 is distorted or undergoes intramolecular exchange as discovered in IF,, then the 12%e-lgF coupling will appear sharply in the n.m.r.…”

Section: Bonding In the Oxide Pentafluoridesmentioning

confidence: 91%

¹⁹F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

Bartlett¹,

Beaton²,

Reeves³

et al. 1964

Can. J. Chem.

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The IgF n.1n.r. spectra of IF?, ReF7, IOFb! ReOF5, and have been recorded. 1F;gives rise to a broad symmetric doublet with a spl~tting of 4 100 f 300 c.p.s. Interpreted as part~ally collapsed and unresolved 19F-1nI coupling. ReF7 gives a single line of width 65 c.p.s. a t low field. These spectra give no information about the molecular structure other than that there is a fast intramolecular process causing magnetic equivalence. IOFs and ReOFb both exhibit a quintet/doublet spectrum indicative of locked C4, symmetry. The multiplet splittings in IOFs are not resolved in pure IOF5 or in IOF5/IF7 mixtures, but can be seen for IOF5 in solution in IF5. The doublet lies t o higher field than the quintet in IOF5, but the reverse occurs in ReOF5. In the paramagnetic molecule OsOFs only the resonance of the unique axial fluorine IS observed, indicative of localization of the non-bonding d-electron in the equitorial plane of the nlolecule.The recent controversy (1,2) over the nlolecular structure of IF7 and the demonstration in these laboratories by infrared studies (3) that much of the earlier work on IF7 was carried out on sa~nplescontaminated with IOFS have made a reinvestigation of the structure of these and related colnpounds desirable. We set out to characterize these molecules by their 19F (n.m.r.) spectra. At the onset of our investigation of the heptafluoride the only previously reported n.m.r. study was fro111 the early work of Gutowsky and Hoffman (4), who, using material of uncertain purity, reported a nlultiple spectrunl which they ascribed to nonequivalent fluorine nuclei. Preparation of the ConzpoundsThe fluorides or oxyfluorides were prepared in all-welded inonel cans provided with Hoke A431 valves joined to them by monel solder tube fittings. The cans were joined t o the fluorine line and the metal vacuum line by way of monel Swagelock fittings provided with Teflon front ferrules and nylon back ferrules.Iodine pentafluoride was made by fluorinating iodine, the reaction being moderated by immersion of the can in cold water. The more volatile fluorides were removed by vacuum distillation.Iodine heptafluoride was best made by fluorinating the distilled pentafluoride with a twofold excess of fluorine a t 200° for a n hour or so. Excess fluorine was removed under vacuum with the can held a t -19G0. Heptafluoride prepared in this way was shown by infrared spectroscopy to be oxyfluoride free.Iodine oxide pentafluoride was most conveniently prepared by the addition of a quantity of water, calculated to satisfy the eq. IF; f H2O -+ IOFG f 2HF, t o the heptafluoride which was measured out tensimetrically, then condensed in a ICelF tube. This tube was joined to the vacuuln system by a flare fitting. Hydrogen fluoride was removed by keeping the products of the reaction over sodium fluoride in a ~nonel can. Indeed, hydrogen fluoride was conveniently removed from all of the fluorides in this way.Rlreniunz oxide pentafluoride was prepared by the fluorination of rhenium dioxide as previously described (5), the r...

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Section: Bonding In the Oxide Pentafluoridesmentioning

confidence: 91%

¹⁹F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

Bartlett¹,

Beaton²,

Reeves³

et al. 1964

Can. J. Chem.

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“…The infrared spectra of the gaseous alkali metal halides to 200 in the salts of the heavier metals were extrapolated from the known radius and force constant data. Klemperer found that the classical ionic model could explain the gaseous molecule spectra.…”

Section: S Mx-type Metal Halidesmentioning

confidence: 99%

Metal Halide Vibrations

Ferraro

1971

Low-Frequency Vibrations of Inorganic and Coordination Compounds

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“…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%

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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Xenon Tetroxide: Preparation and Some Properties

Abstract: Xenon tetroxide is a yellow solid at low temperature. It has a vapor pressure of about 25 mm-Hg at 0 degrees C. It is unstable at room temperature. The infrared spectrum of the vapor shows it to have tetrahedral symmetry.

Cited by 67 publications

References 5 publications

¹⁹F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

¹⁹F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

Metal Halide Vibrations

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

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Xenon Tetroxide: Preparation and Some Properties

Abstract: Xenon tetroxide is a yellow solid at low temperature. It has a vapor pressure of about 25 mm-Hg at 0 degrees C. It is unstable at room temperature. The infrared spectrum of the vapor shows it to have tetrahedral symmetry.

Cited by 67 publications

References 5 publications

19F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

19F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

Metal Halide Vibrations

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

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¹⁹F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

¹⁹F N.M.R. SPECTRA OF HEPTAVALENT FLUORIDES AND OXIDE PENTAFLUORIDES

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