Photochemistry with Chlorine Trifluoride: Syntheses and Characterization of Difluorooxychloronium(V) Hexafluorido(non)metallates(V), [ClOF(2)][MF(6)] (M=V, Nb, Ta, Ru, Os, Ir, P, Sb)

A photochemical route to salts consisting of difluorooxychloronium(V) cations, [ClOF(2)](+), and hexafluorido(non)metallate(V) anions, [MF(6)](−) (M=V, Nb, Ta, Ru, Os, Ir, P, Sb) is presented. As starting materials, either metals, oxygen and ClF(3) or oxides and ClF(3) are used. The prepared compounds were characterized by single‐crystal X‐ray diffraction and Raman spectroscopy. The crystal structures of [ClOF(2)][MF(6)] (M=V, Ru, Os, Ir, P, Sb) are layer structures that are isotypic with the previously reported compound [ClOF(2)][AsF(6)], 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 [ClOF(2)](+) cations of the Nb and Ta compounds occurs. In all compounds reported here, a trigonal pyramidal [ClOF(2)](+) cation with three additional Cl⋅⋅⋅F contacts to neighboring [MF(6)](−) anions is observed, resulting in a pseudo‐octahedral coordination sphere around the Cl atom. The Cl−F and Cl−O bond lengths of the [ClOF(2)](+) cations seem to correlate with the effective ionic radii of the M (V) 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 [MF(6)](−) and the Cl−O Raman shifts also do not generally follow this trend.