Chloryl compounds. Part II. Chloryl hexafluoroarsenate and chloryl fluoride

Abstract

The infrared and Raman spectra of chloryl hexafluoroarsenate have been obtained. The observed vibrations have been interpreted in terms of an ionic compound C10z+AsF6-, where strong cation-anion interaction results in a symmetry lowering of the ion. The compound together with chloryl fluoride produces the chloronium cation C102+(solv) in solution of fluorosulfuric acid. The solvolysis of FC102 is studied by conductometry and 19F nuclear magnetic resonance (n.rn.r.) in order to elucidate the observed anionxation interaction for C1O2AsF6 more fully. 'T n.m.r. studies of FCIO, and related molecules have been used to discuss the bonding in chloronium compounds.

Vibrational and Mössbauer spectra of some hexachloro- and hexafluorostannate complexes

“…48,1970 symmetry effect and suggests strong anion-cation interaction. This is quite in keeping with the spectra reported for ClO,AsF, (1) and ClO,SbF, (2), where the spectrum of the SbF,-group shows a remarkable similarity (1). Such interaction should logically affect the vibrational modes of the cation as well.…”

The vibrational spectra of ClF2SbF6, BrF2SbF6, and ClO2SbF6

“…The interaction results in the stable solid compounds ClF,SbF6 (2,3), BrF,SbF6 (4,5), and C10,SbF6 (6,7). Structural studies have been restricted to the Raman spectrum of ClF,SbF6 (8), an infrared spectrum of C10,SbF6 (9), and an X-ray diffraction study of BrF,SbF6 (10). The structural interpretations of this class of compounds differ quite distinctively.…”

“…The vibrational spectra of the related compounds C102AsF6 (1 1) and ClF,AsF6 (12,13) have been interpreted using a strictly ionic model as evidenced by elaborate force constant calculations. A more cautious approach (8)(9)(10) has found some evidence for anion+ation interaction via fluorine bridge bonding in these compounds.…”