Preparation and characterization of some salts of the difluoro-oxobromine(V) cation

Bougon, R.; Huy, T. Bui; Charpin, P.; Gillespie, R. J.; Spekkens, Paul H.

doi:10.1039/dt9790000006

Cited by 12 publications

(13 citation statements)

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“…Upon coordination of KrF 2 , the cation stretching frequencies shift to lower frequency relative to those of [BrOF 2 ][AsF 6 ]. 35 The highest frequency bands at 1047, 1053 cm -1 are assigned to the factor-group split Br-O stretching mode. The in-phase and out-of-phase BrF 2 stretching bands occur at 644 and 625 cm -1 , respectively, and show no factor-group splitting.…”

Section: Attempts To Form Thementioning

confidence: 98%

“…The two bands are also slightly shifted to lower frequency compared to those observed for free BrOF 2 + . 35 The trends in the cation stretching frequencies can be accounted for by donation of electron density from the KrF 2 ligands to the bromine atom, rendering bromine less electropositive (see Natural Bond Orbital Analyses) and shifting the modes to lower frequency. The cation bands at 314, 371/377, and 397 cm -1 are assigned to BrOF 2 + deformation modes and are in good agreement with the calculated values.…”

Section: Attempts To Form Thementioning

confidence: 99%

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A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF₂][AsF₆]·2KrF₂

et al. 2010

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The synthesis of [BrOF(2)][AsF(6)] x 2 KrF(2), its structural characterization, and bonding are described in this study. Although several KrF(2) adducts with transition metal centers have been previously reported, none have been crystallographically characterized. The solid-state Raman spectrum of [BrOF(2)][AsF(6)] x 2 KrF(2) has been assigned with the aid of quantum-chemical calculations. The low-temperature (-173 degrees C) X-ray crystal structure of [BrOF(2)][AsF(6)] x 2 KrF(2) consists of isolated molecular units and represents an example of KrF(2) coordinated to a main-group atom. The coordination geometry around the BrOF(2)(+) cation renders the free valence electron lone pair more compact than in free BrOF(2)(+). The KrF(2) ligands are coordinated trans to the fluorine atoms of BrOF(2)(+) with the AsF(6)(-) anion coordinated trans to oxygen. The quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF) analyses have been carried out in order to define the nature of the bonding in the complex. A significant amount of charge (0.25 e) is transferred to BrOF(2)(+) from the two KrF(2) ligands (0.10 e each) and from the AsF(6)(-) anion (0.05 e). Significant polarization also occurs within the KrF(2) ligands, which enhances the anionic characters of the fluorine bridges. The interaction energy is mostly governed by the electrostatic interaction of the positively charged bromine atom with the surrounding fluorine atoms.

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Section: Attempts To Form Thementioning

confidence: 98%

Section: Attempts To Form Thementioning

confidence: 99%

A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF₂][AsF₆]·2KrF₂

et al. 2010

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“…ClOF 3 shows Lewis amphoteric behavior, thus it forms adducts with both Lewis acids and Lewis bases [20–22] . The higher homologues, BrOF 3 and IOF 3 , are known to exhibit similar reactivities towards Lewis acids and bases [23–31] . For example, with Lewis bases, alkali metal fluorides and ClOF 3 form compounds containing the tetrafluoridooxidochlorate(V) anion, [ClOF 4 ] − , which is likely tetragonal‐pyramidal like the homologous [ X OF 4 ] − ( X =Br, I) anions are [22, 23, 31, 32] .…”

Section: Introductionmentioning

confidence: 99%

“…[20][21][22] The higher homologues, BrOF 3 and IOF 3 ,a re known to exhibit similar reactivitiest owards Lewis acids and bases. [23][24][25][26][27][28][29][30][31] For example, with Lewisb ases, alkali metal fluorides and ClOF 3 form compounds containing the tetrafluoridooxidochlorate(V)a nion, [ClOF 4 ] À , whichi sl ikely tetragonal-pyramidal like the homologous [XOF 4 ] À (X = Br,I )a nions are. [22,23,31,32] However, ac rystal structure containing [ClOF 4 ] À anions has yet to be determined.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry with Chlorine Trifluoride: Syntheses and Characterization of Difluorooxychloronium(V) Hexafluorido(non)metallates(V), [ClOF₂][MF₆] (M=V, Nb, Ta, Ru, Os, Ir, P, Sb)

Scheibe

Karttunen

Weigend

et al. 2020

Chemistry A European J

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A photochemical route to salts consisting of difluorooxychloronium(V) cations, [ClOF2]+, and hexafluorido(non)metallate(V) anions, [MF6]− (M=V, Nb, Ta, Ru, Os, Ir, P, Sb) is presented. As starting materials, either metals, oxygen and ClF3 or oxides and ClF3 are used. The prepared compounds were characterized by single‐crystal X‐ray diffraction and Raman spectroscopy. The crystal structures of [ClOF2][MF6] (M=V, Ru, Os, Ir, P, Sb) are layer structures that are isotypic with the previously reported compound [ClOF2][AsF6], whereas for M=Nb and Ta, similar crystal structures with a different stacking variant of the layers are observed. Additionally, partial or full O/F disorder within the [ClOF2]+ cations of the Nb and Ta compounds occurs. In all compounds reported here, a trigonal pyramidal [ClOF2]+ cation with three additional Cl⋅⋅⋅F contacts to neighboring [MF6]− anions is observed, resulting in a pseudo‐octahedral coordination sphere around the Cl atom. The Cl−F and Cl−O bond lengths of the [ClOF2]+ cations seem to correlate with the effective ionic radii of the MV ions. Quantum‐chemical, solid‐state calculations well reproduce the experimental Raman spectra and show, as do quantum‐chemical gas phase calculations, that the secondary Cl⋅⋅⋅F interactions are ionic in nature. However, both solid‐state and gas‐phase quantum‐chemical calculations fail to reproduce the increases in the Cl−O bond lengths with increasing effective ionic radius of M in [MF6]− and the Cl−O Raman shifts also do not generally follow this trend.

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“…The pyramidal cations F 2 ClO + and F 2 BrO + are so far the only oxohalide cations for which mean amplitudes of vibration were calculated [103], on the basis of known spectroscopic data [104,105]. Results, at different temperatures, are shown in Table 20.…”

Section: F 2 Xo + Speciesmentioning

confidence: 99%

Mean amplitudes of vibration of molecules and ions with interhalogen bonds and related species

Baran

2008

Journal of Fluorine Chemistry

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Preparation and characterization of some salts of the difluoro-oxobromine(V) cation

Cited by 12 publications

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A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF₂][AsF₆]·2KrF₂

A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF₂][AsF₆]·2KrF₂

Photochemistry with Chlorine Trifluoride: Syntheses and Characterization of Difluorooxychloronium(V) Hexafluorido(non)metallates(V), [ClOF₂][MF₆] (M=V, Nb, Ta, Ru, Os, Ir, P, Sb)

Mean amplitudes of vibration of molecules and ions with interhalogen bonds and related species

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Preparation and characterization of some salts of the difluoro-oxobromine(V) cation

Cited by 12 publications

References 0 publications

A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF2][AsF6]·2KrF2

A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF2][AsF6]·2KrF2

Photochemistry with Chlorine Trifluoride: Syntheses and Characterization of Difluorooxychloronium(V) Hexafluorido(non)metallates(V), [ClOF2][MF6] (M=V, Nb, Ta, Ru, Os, Ir, P, Sb)

Mean amplitudes of vibration of molecules and ions with interhalogen bonds and related species

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A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF₂][AsF₆]·2KrF₂

A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF₂][AsF₆]·2KrF₂

Photochemistry with Chlorine Trifluoride: Syntheses and Characterization of Difluorooxychloronium(V) Hexafluorido(non)metallates(V), [ClOF₂][MF₆] (M=V, Nb, Ta, Ru, Os, Ir, P, Sb)