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Photochemistry with ClF 3 – An Access to [ClOF 2 ] + Salts
Author(s) -
Scheibe Benjamin,
Karttunen Antti J.,
Kraus Florian
Publication year - 2022
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202200106
Subject(s) - monoclinic crystal system , orthorhombic crystal system , triclinic crystal system , crystallography , chemistry , raman spectroscopy , crystal structure , infrared spectroscopy , halide , molecule , x ray crystallography , hydrate , inorganic chemistry , diffraction , organic chemistry , physics , optics
A route to salts of the [ClOF 2 ] + cation is described that does not require the parent fluoride ClOF 3 as a starting material. These can be obtained when either metals such as Cr, Rh, Pd and Au, halides such as PtCl 2 , SnF 2 and PbF 4 , or oxides such as B 2 O 3 , OsO 4 , GeO 2 , SnO and Sb 2 O 4 are reacted with ClF 3 and additional O 2 , where necessary, under UV irradiation. Cr, Rh, Pd, PtCl 2 , GeO 2 , and SnO formed salts with the respective hexafluoridometallate(IV) anion with the composition [ClOF 2 ] 2 [ M F 6 ]. They crystallize in two distinct structure types in either the monoclinic crystal system ( M =Cr, Rh, Ge) or the orthorhombic one ( M =Pd, Pt, Sn). The fluorides SnF 2 and PbF 4 were converted to the monoclinic salts [ClOF 2 ] M F 5 , and B 2 O 3 formed orthorhombic [ClOF 2 ][BF 4 ]. The triclinic compound ([ClOF 2 ][OsO 3 F 3 ]) 2 ⋅OsF 6 was obtained from OsO 4 and contains a neutral co‐crystallized OsF 6 molecule. A monoclinic double salt with the composition [ClOF 2 ] 2 [AuF 4 ][SbF 6 ] was obtained by reacting a mixture of Sb 2 O 4 and Au. The compounds were investigated by single crystal X‐ray diffraction and IR and Raman spectroscopy. Quantum‐chemical calculations for the solid‐state allowed for the band assignments of the vibrational spectra.