In:
Chemistry – A European Journal, Wiley, Vol. 27, No. 7 ( 2021-02), p. 2381-2392
Abstract:
A photochemical route to salts consisting of difluorooxychloronium(V) cations, [ClOF 2 ] + , and hexafluorido(non)metallate(V) anions, [ M F 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 ][ M F 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 [ M F 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 [ M F 6 ] − and the Cl−O Raman shifts also do not generally follow this trend.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.202003629
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
1478547-X
