Preparation of Transition Metal Fluorides using ClF
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Haiges, Ralf

doi:10.1002/9781118409466.ch18

Efficient Preparations of Fluorine Compounds 2012

DOI: 10.1002/9781118409466.ch18

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Preparation of Transition Metal Fluorides using ClF ₃

Ralf Haiges

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Cited by 4 publications

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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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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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Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

et al. 2020

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Difluorochloronium(III) compounds were synthesized from the reaction of metal powders (Ru, Os, Ir, Au), metal fluorides (NbF5, SbF3, BiF5) or a metal chloride (TaCl5) with excess liquid chlorine trifluoride. The compounds ClF2[AuF4], ClF2[MF6] (M = Nb, Ta, Ru, Os, Ir, Sb, Bi) and ClF2[Ta2F11] were obtained in crystalline form and their crystal structures were determined by single‐crystal X‐ray diffraction. The ClF2+ cations in the investigated compounds are bent, containing two strong, short, mainly covalent Cl–F bonds and two sterically active, free valence electron pairs in a pseudo‐tetrahedral arrangement. The coordination around the Cl atom is extended by two highly ionic, long fluorine bridges to neighboring fluoridometallate anions, resulting in a total coordination number of six. The crystal structures vary among the ClF2+ compounds and range from molecular building blocks, such as dimeric (ClF2[AuF4])2 and (ClF2[Ta2F11])2, to chains, some of which being helical, as in ClF2[MF6], (M = Nb, Ta, Ru, Os, Ir, Sb, Bi). Quantum‐chemical solid‐state and gas‐phase calculations were carried out to elucidate the bonding within the ClF2+ cations and their interactions with the bridging F atoms.

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Reactions of ClF₃ with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

2020

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Compounds containing the dioxychloronium cation, [ClO 2 ] + , were obtained from reactions of ClF 3 with various oxides such as TiO 2 , MoO 3 , Re 2 O 7 , SnO, P 2 O 5 , As 2 O 5 , and Nb metal, as the latter contained oxide as an impurity. Partial hydrolysis of [ClF 2 ] [IrF 6 ] led to the formation of [ClO 2 ][IrF 6 ]. The crystal structures of the compounds were determined by single-crystal X-ray diffraction, which showed that depending on the starting material [ClO 2 ] + salts with the fluoridometallate anions [TiF 3/2 F 3/

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Preparation of Transition Metal Fluorides using ClF ₃

Cited by 4 publications

References 12 publications

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)

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

Reactions of ClF₃ with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

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Preparation of Transition Metal Fluorides using ClF 3

Cited by 4 publications

References 12 publications

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)

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

Contact Info

Product

Resources

About

Preparation of Transition Metal Fluorides using ClF ₃

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)

Reactions of ClF₃ with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates