Abstract
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 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 [MF6]− and the Cl−O Raman shifts also do not generally follow this trend.
Highlights
A photochemical route to salts consisting of difluorooxychloronium(V) cations, [ClOF2]+, and hexafluorido(non)metallate(V) anions, [MF6]À (M = V, Nb, Ta, Ru, Os, Ir, P, Sb) is presented
Both solid-state and gas-phase quantumchemical calculations fail to reproduce the increases in the ClÀO bond lengths with increasing effective ionic radius of M in [MF6]À and the ClÀO Raman shifts do not generally follow this trend
The reactions of chlorine trifluoride with oxides or with metals and O2 under UV irradiation led to the formation of the compounds [ClOF2][MF6] (M = V, Nb, Ta, Ru, Os, Ir, P, Sb)
Summary
1965, a few years before the first publications on ClOF3 appeared in the open literature.[1,2,16,17,18] It can either be synthesized by the fluorination of ClONO2 or of Cl2O at low temperatures according to Equations (1) and (2).[2,17]. In the case of the oxides, the initial reaction is likely the formation of ClO2F and the dissolved pentafluoride, which subsequently will form a solvated [ClO2][MF6] (M = V, Nb, Ta, Ru, P, Sb) salt. The formation of ClO2F from the reaction of ClF3 with oxides such as H2O, A[ClO3] (A = Na, K), [UO2]F2 and Cs[IOF4] has been reported.[10,42,43,44,45] The Lewis base character of ClO2F has been previously described, where a range of Lewis acids, compounds, such as [ClO2][BF4], [ClO2]GeF5 and [ClO2][MF6] (M = Ru, P, As, Sb), were obtained.[39,46,47,48,49] As mentioned above, ClOF3 is formed in photochemical reactions, which will likely displaces [ClO2]+ as ClO2F to form a [ClOF2]+ salt.
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