Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)




R.J. Gillespie


A number of new compounds containing polyatomic cations of the chalcogens have been prepared and their structures investigated. In particular methods for preparing heteroatomic cations containing two of the elements in the same cation have been extensively studied for the first time. Particular emphasis has been given to the preparation of crystalline samples suitable for the investigation of structure by x-ray crystallography. In addition some structural studies have been made by Raman spectroscopy.

The following compounds containing homopolyatomic cations have been prepared by the reaction of ASF₅ or SbF₅ with the appropriate element in solution in SO₂ and their structures investigated: S₁₆(AsF₆)₂, Se₁₀(AsF₆)₂, Te₆(SbF₆)₂, and TeAsF₆. By reactions between two different homopolyatomic cations or by reactions of a single homopolyatomic cation with one of the elements sulphur, selenium or tellurium the following compounds of new heteropolyatomic cations were prepared and their structures studied. Te₂Se₈(AsF₆)₂.SO₂, Te₃.₇Se₆.₃(AsF₆)₂, Te₂Se₂(AsF₆)₂, Te₃S₃(AsF₆)₂ and S₂Se₈(AsF₆)₂.

In a rather limited investigation of the reactions of bismuth with AsF₅ and SbF₅ the following compounds containing the Bi₅³⁺ cation have been prepared and characterized by Raman spectroscopy: Bi₅(AsF₆)₃2SO₂ and Bi₅(SbF₆)₃. A polymeric compound of composition BiF₂.AsF₆ was also prepared.

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