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UBC Theses and Dissertations

Spectral and magnetic studies on metal fluorosulfate complexes Alleyne, Carl Stanley


The work described in this thesis is in two essentially independent parts. In Chapter 3, we have studied the infrared spectra of the alkaline earth and first-row transition metal bisfluorosulfates over the frequency range 4000 – 250 cm⁻¹ in an attempt to resolve discrepancies in the literature on the infrared spectra of these compounds. We have obtained spectra for these compounds which are easily assigned and we suggest that the discrepancies in the literature may be due to differences in crystalline modifications studied by the different workers. We have also checked the reliability of infrared frequency shifts as measures of cation-anion interaction in fluorosulfate compounds. We observe a general increase in frequencies for the symmetric SO₃ stretching and S-F stretching modes with increasing interaction, but no quantitative relationship is present. However, the S-F stretching mode is shown to give a good indication of cation-anion interaction for compounds with predominantly ionic character. In the second part of this thesis, described in Chapter 4, we have prepared tetrakis(pyridine) complexes of nickel(II), copper(II) and zinc(II) fluorosulfates. In order to determine the coordination strength of the fluorosulfate ion relative to other ions, we have also prepared and characterized complexes of the general formula Cu(py) ₄X₂ (X = C10₄ˉ, BF₄ˉ, N0₃ˉ, CH₃C₆H₄SO₃ˉ, CF₃COOˉ ) by infrared, electronic, and electron paramagnetic resonance spectroscopy, electrical conductivity, and magnetic susceptibility measurements. The results indicate that on the whole, the coordination strength of SO₃Fˉ towards metals is similar, but slightly stronger than CIO₄ˉ and BF₄ˉ , definitely stronger than PF₆ˉ, and weaker than ReO₄,ˉ, CH₃C₆H₄SO₃ˉ and CF₃C00ˉ .

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