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

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