Synthesis and characterization of CrF4O, KrF2.CrF4O, and NO+CrF5O-

Christe, Karl O.; Wilson, William W.; Bougon, R.

doi:10.1021/ic00233a013

Cited by 38 publications

(58 citation statements)

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“…[22] Although these workers isolated CrO 2 F 2 in high purity and high yield, product recovery was complicated by the competing reverse hydrolysis reaction [Eq. [20] The present study,h owever, shows the KrF 2 /CrOF 4 systemi s more complex. This necessitated as eries of low-temperature recrystallizations and decantationso ft he HF supernatant to achieve an acceptable level of purity.Int he present work, millimole quantities of CrO 2 F 2 were also conveniently prepared at room temperature in quantitative yield by use of am odified procedure in which excessF 2 gas wasu sed to oxidatively fluorinate the solvolytic water produced in [Eq.…”

Section: Syntheses and Propertiesmentioning

confidence: 59%

“…The observeda nd calculated frequencies and their assignmentsa re provided in Ta bles S2-S5. [20] Overall, the experimentalv ibrationalf re-quencies and their trends are well reproducedb yt he calculated frequencies. Spectrala ssignments were made by comparison with the calculated vibrational frequencies and Raman intensities of the energy-minimized, gas-phase geometries of NgF 2 ·CrOF 4 (C s ) and NgF 2 ·2CrOF 4 (C 1 , syn-conformation).…”

Section: Raman Spectroscopymentioning

confidence: 59%

“…Aversion of the latter synthetic procedure was previously reported by Engelbrecht and Grosse. [20] Unlike the direct fluorination of CrO 3 with F 2 , [23,28] this synthetic route providedC rOF 4 that is free of CrO 2 F 2 and CrF 5 .F urthermore, KrF 2 ·CrOF 4 was also formed when a2 :1 molar ratio of KrF 2 /CrO 2 F 2 was used. (2)], which wasf avored when HF solvent was removed under dynamic vacuum.…”

Section: Syntheses and Propertiesmentioning

confidence: 99%

“…[20] The KrF 2 adduct was obtaineda sa ni ntermediate in an improved synthesis in which CrOF 4 was formed by oxidative fluorination of CrO 2 F 2 with KrF 2 and was structurally characterized by LT Raman and infrared spectroscopy.I nc ontrast with KrF 2 ·nMoOF 4 (n = 1-3) and KrF 2 ·WOF 4 ,t he 19 FNMR spectrum of KrF 2 ·CrOF 4 in SO 2 ClF at À10 to À120 8Cfailed to provide evidencef or anonlabile, fluorine-bridged adduct, but showedt hat the adduct dissociates in solution to give two sharp signals corresponding to KrF 2 and CrOF 4 . [20] The KrF 2 adduct was obtaineda sa ni ntermediate in an improved synthesis in which CrOF 4 was formed by oxidative fluorination of CrO 2 F 2 with KrF 2 and was structurally characterized by LT Raman and infrared spectroscopy.I nc ontrast with KrF 2 ·nMoOF 4 (n = 1-3) and KrF 2 ·WOF 4 ,t he 19 FNMR spectrum of KrF 2 ·CrOF 4 in SO 2 ClF at À10 to À120 8Cfailed to provide evidencef or anonlabile, fluorine-bridged adduct, but showedt hat the adduct dissociates in solution to give two sharp signals corresponding to KrF 2 and CrOF 4 .…”

Section: Introductionmentioning

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: 59%

Section: Raman Spectroscopymentioning

confidence: 59%

Section: Syntheses and Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

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 KrF þ cation is among the most powerful chemical oxidants known (191) and is capable of oxidizing gaseous xenon to XeF þ 5 ; gaseous oxygen to O þ 2 ; NF 3 to NF þ 4 (189); and chlorine, bromine, and iodine pentafluorides to the ClF þ 6 , BrF þ 6 , and lF þ 6 cations, respectively (189,190,(192)(193)(194). (105,195). The only example presently known in which KrF 2 coordinates to a main-group center is [BrOF 2 ][AsF 6 ]Á2KrF 2 [1217521- and is the only coordination compound of KrF 2 that has been structurally characterized by x-ray crystallography (196).…”

Section: Krypton Compoundsmentioning

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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Chromium Compounds

Page¹,

Loar²

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Chromium compounds and their important uses are described. Chemical properties of the low valence compounds, Cr(‐II) through Cr(I), and those of Cr(IV) and Cr(V) are discussed as are those of the commercially important oxidation states of Cr(II), Cr(III), and Cr(VI). Sodium chromate and dichromate production from imported chromite ore, and the production of other chromates, dichromates, and chromic acid are summarized. The manufacture of water‐soluble trivalent compounds is also given. Regulations concerning shipments, specifications, and analytical test methods are discussed as are the health and safety factors of chromium compounds. The environmental impact and waste management practices of chromium compounds is also of importance. Chromium compounds of various oxidation states are used commercially as pigments, in metal finishing, leather tanning, drilling muds, and in wood preservation. Chromium compounds are also used in alloys, batteries catalists, photosensitive gels, and as reagent grade chemicals.

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Synthesis and characterization of CrF4O, KrF2.CrF4O, and NO+CrF5O-

Cited by 38 publications

References 0 publications

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)_∞

Noble‐Gas Compounds

Chromium Compounds

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Synthesis and characterization of CrF4O, KrF2.CrF4O, and NO+CrF5O-

Cited by 38 publications

References 0 publications

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)∞

Noble‐Gas Compounds

Chromium Compounds

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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)_∞