A Raman spectroscopic study of the XeOF4/XeF2 system and the X-ray crystal structure of α-XeOF4·XeF2

Hughes, Michael J.; Brock, David S.; Mercier, Hélène P. A.; Schrobilgen, Gary J.

doi:10.1016/j.jfluchem.2011.05.010

Cited by 20 publications

(13 citation statements)

References 48 publications

(44 reference statements)

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“…The bond lengths and bond angles around the Xe atom of XeOF 4 in 5 are comparable to those of XeOF 4 ⋅XeF 2 . As is the case for the isoelectronic [XeF 5 ] + cation (vide supra) and XeOF 4 ⋅XeF 2 , the four Xe‐ ‐ ‐F contacts with the Xe atom of XeOF 4 in [XeF 5 ] 2 [Cr 2 O 2 F 8 ] ⋅ 2 XeOF 4 ( 5 ) (2.968(1) Å, 2.986(1) Å, 3.337(1) Å, 3.496(1) Å) occur in the open square face of the square‐pyramidal XeOF 4 molecule and avoid the valence electron lone pair of Xe that is trans to the oxygen atom.…”

Section: Resultsmentioning

confidence: 83%

“…Spectral assignments were made by comparison with the calculated vibrational frequencies and intensities of the energy‐minimized, gas‐phase geometries of [XeF 5 ] 2 [Cr 2 O 2 F 8 ] ⋅ 2 XeOF 4 ( 5 ) and [XeF 5 ][Xe 2 F 11 ][CrOF 5 ] ⋅ 2 CrOF 4 ( 6 ) at the uPBE1PBE/aug‐cc‐pVDZ‐Def2SVP level of theory. Vibrational assignments for CrOF 4 , XeOF 4 , and the [XeF 5 ] + and [Xe 2 F 11 ] + cations were also aided by comparison with polymeric CrOF 4 , XeOF 4 ⋅XeF 2 , [XeF 5 ][OsO 3 F 3 ], [XeF 5 ][AsF 6 ], [XeF 5 ][BF 4 ], [ 71] [Xe 2 F 11 ][AuF 6 ], [Xe 2 F 11 ][PdF 6 ], and [Xe 2 F 11 ][OsO 3 F 3 ] . The observed and calculated frequencies, their detailed assignments, and mode descriptions are provided in Tables S7 and S8, Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

“…The bond lengths and bond anglesa round the Xe atom of XeOF 4 in 5 are comparable to those of XeOF 4 ·XeF 2 . [67] As is the case for the isoelectronic [XeF 5 ] + cation (vide supra) and (6) ), [12] and XeF 2 ·2CrOF 4 (Cr(2)---F(1), 2.386 (1) ). [ (3) )h ave significant double-bond character and are comparable in length to those of a-CrOF 4 (1.539(3)-1.558(4) ), [12] b-CrOF 4 (1.5490 (7) ), [12] and XeF 2 ·2CrOF 4 (1.545 (2) ).…”

Section: Xeofmentioning

confidence: 99%

“…The elongated bond is attributed to the trans-influence of oxygen and to three Xe-F ax contacts (Xe(1)---F(1), 2.463(2) ; Xe(2)---F(1), 2.822(2) ;X e(3)---F(1), 2.826(2) )w ith the xenon atomso fn eighboring cations( vide supra (2) )i sc omparable to those of CrOF 3 (1.542 (5) ), [42] a-CrOF 4 (1.539(3)-1.558(4) ), and b-CrOF 4 (1.5490 (7) ). [12] Raman spectroscopy (6) at the uPBE1PBE/aug-cc-pVDZ-Def2SVPl evel of theory.V ibrational assignments for CrOF 4 ,X eOF 4 ,a nd the [XeF 5 ] + and [Xe 2 F 11 ] + cationsw ere also aided by comparison with polymeric CrOF 4 , [12] XeOF 4 ·XeF 2 , [67] [XeF 5 ][OsO 3 F 3 ], [51] [XeF 5 ][AsF 6 ], [70] [XeF 5 ][BF 4 ], [71] [Xe 2 F 11 ][AuF 6 ], [53] [Xe 2 F 11 ][PdF 6 ], [53] and [Xe 2 F 11 ] [OsO 3 F 3 ]. [51] The observed and calculated frequencies, their detailed assignments,a nd mode descriptions are provided in Tables S7 and S8, Supporting Information.…”

Section: Xeofmentioning

confidence: 99%

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Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF₅]⁺ and [Xe₂F₁₁]⁺ Salts of the [Cr^VIOF₅]⁻, [Cr^VOF₅]²⁻, [Cr^V₂O₂F₈]²⁻, and [Cr^IVF₆]²⁻ Anions

Goettel

Bortolus

Stuart

et al. 2019

Chemistry A European J

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Molten mixtures of XeF6 and CrVIOF4 react by means of F2 elimination to form [XeF5][Xe2F11][CrVOF5]⋅2 CrVIOF4, [XeF5]2[CrIVF6]⋅2 CrVIOF4, [Xe2F11]2[CrIVF6], and [XeF5]2[CrV2O2F8], whereas their reactions in anhydrous hydrogen fluoride (aHF) and CFCl3/aHF yield [XeF5]2[CrV2O2F8]⋅2 HF and [XeF5]2[CrV2O2F8]⋅2 XeOF4. Other than [Xe2F11][MVIOF5] and [XeF5][MVI2O2F9] (M=Mo or W), these salts are the only Group 6 oxyfluoro‐anions known to stabilize noble‐gas cations. Their reaction pathways involve redox transformations that give [XeF5]+ and/or [Xe2F11]+ salts of the known [CrVOF5]2− and [CrIVF6]2− anions, and the novel [CrV2O2F8]2− anion. A low‐temperature Raman spectroscopic study of an equimolar mixture of solid XeF6 and CrOF4 revealed that [Xe2F11][CrVIOF5] is formed as a reaction intermediate. The salts were structurally characterized by LT single‐crystal X‐ray diffraction and LT Raman spectroscopy, and provide the first structural characterizations of the [CrVOF5]2− and [CrV2O2F8]2− anions, where [CrV2O2F8]2− represents a new structural motif among the known oxyfluoro‐anions of Group 6. The X‐ray structures show that [XeF5]+ and [Xe2F11]+ form ion pairs with their respective anions by means of Xe‐ ‐ ‐F–Cr bridges. Quantum‐chemical calculations were carried out to obtain the energy‐minimized, gas‐phase geometries and the vibrational frequencies of the anions and their ion pairs and to aid in the assignments of their Raman spectra.

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Section: Resultsmentioning

confidence: 83%

Section: Resultsmentioning

confidence: 99%

Section: Xeofmentioning

confidence: 99%

Section: Xeofmentioning

confidence: 99%

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Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF₅]⁺ and [Xe₂F₁₁]⁺ Salts of the [Cr^VIOF₅]⁻, [Cr^VOF₅]²⁻, [Cr^V₂O₂F₈]²⁻, and [Cr^IVF₆]²⁻ Anions

Goettel

Bortolus

Stuart

et al. 2019

Chemistry A European J

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“…The bond lengths and bond angles around Xe are comparable to those of XeOF4•XeF2. 35 avoiding the valence electron lone pair that is trans to oxygen.…”

Section: Xeof4mentioning

confidence: 99%

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [Cr(VI)OF5]–, [Cr(IV)F6]2–, [Cr(V)OF5]2–, and [Cr(V)2O2F8]2– Anions

Stuart¹,

Bortolus²,

Goettel³

et al. 2018

Preprint

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Molten mixtures of XeF6 and CrVIOF4 in 1:1 and 1:2 molar ratios undergo reduction to Cr(V) and Cr(IV) by means of F2 elimination to form [XeF5][Xe2F11][CrVOF5]∙2CrVIOF4 and [XeF5]2[CrIVF6]∙2CrVIOF4, respectively, as shown by low-temperature (LT) single-crystal X-ray diffraction (SCXRD). A LT Raman spectroscopic study of an equimolar mixture of solid XeF6 and CrOF4 and its melt showed that [CrVIOF5]– is formed as an intermediate. Reaction of [XeF5]2[CrIVF6]∙2CrVIOF4 with XeF6 in a melt gave [Xe2F11]2[CrIVF6] and [XeF5]2[CrV2O2F8]. Their LT crystal structures revealed that [XeF5]+ and [Xe2F11]+ are coordinated to their respective [CrF6]2− and [Cr2O2F8]2− anions by means of Xe---F–Cr bridges to form infinite chain structures. The reactions of a 1:1 molar ratio of XeF6 and CrOF4 in anhydrous hydrogen fluoride (aHF) and in mixed CFCl3/aHF solvents yielded [XeF5]2[CrV2O2F8]∙2HF and a mixture of [XeF5]2[CrV2O2F8]∙2HF and [XeF5]2[CrV2O2F8]∙2XeOF4, respectively. The SCXRD structures of the latter and aforementioned salts provide the first X-ray structures of [CrOF5]2– and [Cr2O2F8]2–. The [XeF5]2[CrV2O2F8]∙2XeOF4 and [XeF5][Xe2F11][CrVOF5]∙2CrVIOF4 salts were also characterized by LT Raman spectroscopy. Quantum-chemical calculations were carried out to obtain the energy-minimized, gas-phase geometries and vibrational frequencies for [CrVIOF5]–, [XeF5]2[CrV2O2F8]∙2XeOF4, [CrV2O2F8]2–, [XeF5][Xe2F11][CrVOF5]∙2CrVIOF4, [CrVOF5]2–, and to aid in the assignments of their vibrational frequencies.

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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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A Raman spectroscopic study of the XeOF4/XeF2 system and the X-ray crystal structure of α-XeOF4·XeF2

Cited by 20 publications

References 48 publications

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF₅]⁺ and [Xe₂F₁₁]⁺ Salts of the [Cr^VIOF₅]⁻, [Cr^VOF₅]²⁻, [Cr^V₂O₂F₈]²⁻, and [Cr^IVF₆]²⁻ Anions

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF₅]⁺ and [Xe₂F₁₁]⁺ Salts of the [Cr^VIOF₅]⁻, [Cr^VOF₅]²⁻, [Cr^V₂O₂F₈]²⁻, and [Cr^IVF₆]²⁻ Anions

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [Cr(VI)OF5]–, [Cr(IV)F6]2–, [Cr(V)OF5]2–, and [Cr(V)2O2F8]2– Anions

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A Raman spectroscopic study of the XeOF4/XeF2 system and the X-ray crystal structure of α-XeOF4·XeF2

Cited by 20 publications

References 48 publications

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [CrVIOF5]−, [CrVOF5]2−, [CrV2O2F8]2−, and [CrIVF6]2− Anions

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [CrVIOF5]−, [CrVOF5]2−, [CrV2O2F8]2−, and [CrIVF6]2− Anions

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF5]+ and [Xe2F11]+ Salts of the [Cr(VI)OF5]–, [Cr(IV)F6]2–, [Cr(V)OF5]2–, and [Cr(V)2O2F8]2– Anions

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Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF₅]⁺ and [Xe₂F₁₁]⁺ Salts of the [Cr^VIOF₅]⁻, [Cr^VOF₅]²⁻, [Cr^V₂O₂F₈]²⁻, and [Cr^IVF₆]²⁻ Anions

Chromium Oxide Tetrafluoride and Its Reactions with Xenon Hexafluoride; the [XeF₅]⁺ and [Xe₂F₁₁]⁺ Salts of the [Cr^VIOF₅]⁻, [Cr^VOF₅]²⁻, [Cr^V₂O₂F₈]²⁻, and [Cr^IVF₆]²⁻ Anions