Chlorine trifluoride oxide. II. Photochemical synthesis

Pilipovich, Donald; Rogers, H. H.; Wilson, Richard D.

doi:10.1021/ic50115a041

Cited by 22 publications

(18 citation statements)

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“…A photochemical synthesis of ClOF 3 is also possible [1, 16, 18, 19] . ClOF 3 can be obtained at room temperature by UV irradiation of ClF 3 /OF 2 mixtures [1] .…”

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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“…A photochemical synthesis of ClOF 3 is also possible [1, 16, 18, 19] . ClOF 3 can be obtained at room temperature by UV irradiation of ClF 3 /OF 2 mixtures [1] .…”

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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“…However, they are usually stable at the room temperature under certain conditions. Many investigations have been performed to study halogen fluorides, such as ClFO 3 [8], ClF 3 O [9][10][11][12][13][14][15][16][17], ClF 3 O 2 [18][19][20], and BrF 3 O [17,21]. The adducts of ClFO 2 , e.g., ClFO 2 BF 3 and ClFO 2 AsF 5 were also studied and found to exist in ionic structures ClO 2 + BF 4 − and ClO 2 + AsF 6 − , respectively [22].…”

Section: Introductionmentioning

confidence: 99%

A theoretical prediction of thermodynamic properties of chlorine fluorides

Du¹,

Liu²,

Wang³

et al. 2011

Thermochimica Acta

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“…The oxide of ClF 3 , chlorine trifluoride oxide (ClF 3 O) has some similar properties with ClF 3 . Many investigations have been performed to study its preparation, vibrational spectrum, thermodynamic properties, and reactions7–14. With Lewis acid boron trifluoride (BF 3 ), a white crystalline adduct (ClF 2 OBF 4 ) was formed.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study on the adduct of chlorine trifluoride oxide and boron trifluoride—molecular and crystal structures, vibrational spectrum, and thermodynamic properties

Wang

Gong

et al. 2011

Int J of Quantum Chemistry

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To search for the most stable form and understand the relationship between the structure and property of the adduct of chlorine trifluoride oxide and boron trifluoride, various isomeric structures were constructed and optimized with the first principle methods. The most stable structure of the adduct has an ionic form. The vibrational spectra were calculated and assigned, and used to compute the standard thermodynamic properties. Molecular mechanics method was employed to predict the possible crystal packing of the adduct, and density functional theory method was used to refine the crystal structure and to calculate the energy band. The obtained band gap (3.40 eV) shows that the crystal is insensitive and stable under closed environment as was found experimentally.

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Chlorine trifluoride oxide. II. Photochemical synthesis

Cited by 22 publications

References 1 publication

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)

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)

A theoretical prediction of thermodynamic properties of chlorine fluorides

Theoretical study on the adduct of chlorine trifluoride oxide and boron trifluoride—molecular and crystal structures, vibrational spectrum, and thermodynamic properties

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Chlorine trifluoride oxide. II. Photochemical synthesis

Cited by 22 publications

References 1 publication

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)

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)

A theoretical prediction of thermodynamic properties of chlorine fluorides

Theoretical study on the adduct of chlorine trifluoride oxide and boron trifluoride—molecular and crystal structures, vibrational spectrum, and thermodynamic properties

Contact Info

Product

Resources

About

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)

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)