Chemistry of chromyl fluoride.  5.  New preparative routes to chromyl fluoride

Green, Patrick J.; Gard, Gary L.

doi:10.1021/ic50171a055

Cited by 23 publications

(17 citation statements)

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“…[21][22][23][24][25][26][27] In the presentw ork, CrO 2 F 2 was synthesized by reaction of MoF 6 with CrO 3 at approximately 140 8Cu sing a modification of the procedure described by Green and Gard. [21][22][23][24][25][26][27] In the presentw ork, CrO 2 F 2 was synthesized by reaction of MoF 6 with CrO 3 at approximately 140 8Cu sing a modification of the procedure described by Green and Gard.…”

Section: Syntheses and Propertiesmentioning

confidence: 99%

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Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Mercier

Breddemann

Brock

et al. 2019

Chemistry A European J

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The noble‐gas difluoride adducts, NgF2⋅CrOF4 and NgF2⋅2CrOF4 (Ng=Kr and Xe), have been synthesized and structurally characterized at low temperatures by Raman spectroscopy and single‐crystal X‐ray diffraction. The low fluoride ion affinity of CrOF4 renders it incapable of inducing fluoride ion transfer from NgF2 (Ng=Kr and Xe) to form ion‐paired salts of the [NgF]+ cations having either the [CrOF5]− or [Cr2O2F9]− anions. The crystal structures show the NgF2⋅CrOF4 adducts are comprised of Ft−Ng−Fb‐ ‐ ‐Cr(O)F4 structural units in which NgF2 is weakly coordinated to CrOF4 by means of a fluorine bridge, Fb, in which Ng−Fb is elongated relative to the terminal Ng−Ft bond. In contrast with XeF2⋅2MOF4 (M=Mo or W) and KrF2⋅2MoOF4, in which the Lewis acidic, F4(O)M‐ ‐ ‐Fb‐ ‐ ‐M(O)F3 moiety coordinates to Ng through a single M‐ ‐ ‐Fb−Ng bridge, both fluorine ligands of NgF2 coordinate to CrOF4 molecules to form F4(O)Cr‐ ‐ ‐Fb−Ng−Fb‐ ‐ ‐Cr(O)F4 adducts in which both Ng−Fb bonds are only marginally elongated relative to the Ng−F bonds of free NgF2. Quantum‐chemical calculations show that the Cr−Fb bonds of NgF2⋅CrOF4 and NgF2⋅2CrOF4 are predominantly electrostatic with a small degree of covalent character that accounts for their nonlinear Cr‐ ‐ ‐Fb−Ng bridge angles and staggered O−Cr‐ ‐ ‐Fb−Ng−Ft dihedral angles. The crystal structures and Raman spectra of two CrOF4 polymorphs have also been obtained. Both are comprised of fluorine‐bridged chains that are cis‐ and trans‐fluorine‐bridged with respect to oxygen.

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Section: Syntheses and Propertiesmentioning

confidence: 99%

“…[21] Chromyl fluoride was stored at À78 8Cu ntil used. [21] Chromyl fluoride was stored at À78 8Cu ntil used.…”

Section: Synthesesmentioning

confidence: 99%

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Mercier

Breddemann

Brock

et al. 2019

Chemistry A European J

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“…The [CrOF 5 ] À anion has been synthesized as its Cs + salt by heating a1 :1 molar mixture of CsF and CrOF 4 to 100 8C[ Eq. (1)]. [4] Elemental analysisa nd the IR spectrum of the product were in good agreement with the formulation,C s[CrOF 5 ].…”

Section: Introductionmentioning

confidence: 75%

“…Chromyl fluoride (CrO 2 F 2 ) was prepared by reaction of CrO 3 with MoF 6 according to the published procedure . Chromium oxide tetrafluoride was synthesized using a modification of a previously reported procedure that was based on the procedure published by Christe et al …”

Section: Methodsmentioning

confidence: 99%

“…The chromium(VI) oxide fluorides, CrO 2 F 2 [1,2] and CrOF 4 , [3][4][5] and salts of the [CrO 3 F] À , [6][7][8] [CrO 2 F 3 ] À , [9] cis-[CrO 2 F 4 ] 2À , [3,10,11] and [CrOF 5 ] À [4,5] anions have been synthesized and characterized. Synthetic and structural studies have shown that CrOF 4 is sufficiently Lewis acidic to form stable adducts with the noble-gas difluorides NgF 2 (Ng = Kr, [5,12] Xe [12] )( vide infra).…”

Section: Introductionmentioning

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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Chromium Difluoride Dioxide (Chromyl Fluoride)

Gard

Williamson

1986

Inorganic Syntheses

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Chemistry of chromyl fluoride. 5. New preparative routes to chromyl fluoride

Cited by 23 publications

References 1 publication

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

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 Difluoride Dioxide (Chromyl Fluoride)

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Chemistry of chromyl fluoride. 5. New preparative routes to chromyl fluoride

Cited by 23 publications

References 1 publication

Syntheses, Structures, and Bonding of NgF2⋅CrOF4, NgF2⋅2CrOF4(Ng=Kr, Xe), and (CrOF4)∞

Syntheses, Structures, and Bonding of NgF2⋅CrOF4, NgF2⋅2CrOF4(Ng=Kr, Xe), and (CrOF4)∞

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 Difluoride Dioxide (Chromyl Fluoride)

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Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

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