The structure of the solid adducts of SF4 with several fluoride acceptors has been studied by investigations of the "F exchange between SI8F4 and BF3 and between SF4 and BIgF4, the infrared spectrum of SF4.BF3, and the Raman spectra of SF,.BF3, SF4.PF5, SF4.AsF5, and SF4.SbF5. The experimental observations are best accounted for in terms of an ionic structure SF3+.MX,,-in each case, but there is good evidence for relatively strong fluorine bridging between the ions.In anhydrous hydrogen fluoride solution, SF, and the adducts SF,.BF3 and SF,.SbF5 were studied conductimetrically and by "F nuclear magnetic resonance. Both methods indicate con~plete ionization of the adducts to SF3+ and the complex fluoroanion. SF4 is a weak base in hydrogen fluoride ionizing to SF3+ and HF2-.

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The vibrational assignments of the trifluorosulfur (IV) cation (SP3+, previously determined from spectra of solids, are confirmed by polarization measurements on solutions of SF3+BF4-, SF3+PF6-, and SF3+AsF6- in anhydrous HF. Techniques and equipment have been developed to obtain Raman spectra of species dissolved in anhydrous hydrogen fluoride. Accurate polarization information can be obtained even though the FEP fluorocarbon plastic used as a container and window material is optically active.

Swmrrcary It is shown that the adducts SOF,.AsF, and SOF,-SbF, have the ionic structure SOF,+MF,-in the solid state and in solution in hydrogen fluoride: the vibrational spectrum of the SOF,+ ion is assigned and the bonding in the ion is discussed.

The 19F nmr spectra of the following systems have been studied over a range of temperature: AsF,-S02F2, ASF~-SOF~-SO~F~, AsFS-SOZFCl, AsFAO,-SO,F,, AsF6-CH,SO2F-SO2F2, and AsFS-CH3SO2F-SO2F2-SO,. It has been found that AsFs forms very labile complexes with SOF,, SO2, SOaFCI, and CH3S02F, but no complex formation was observed with S02F2.