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A study of some Di- and Tri-atomic halogen and interhalogen cations Wilson, William Wayne


This study is primarily concerned with the cationic halogen derivatives iodine (I)- and bromine (I)- fluorosulfate, their structural and chemical properties, and their use as precursors in the formation of polyhalogen and polyinterhalogen cations. Infrared spectroscopy at 80°K is used to record the vibrational spectrum of IOSO₂F. A consistent assignment is presented for all halogen (I)- fluorosulfates, XOSO₂F where X = F, Cl, Br and I. Evidence for intermolecular association is found in the spectra of IOSO₂F and BrOSO₂F. The addition of diatomic halogens (I₂, Br₂, Cl₂) or interhalogens (IBr, ICI) to IOSO₂F results in the formation of polyhalogen and polyinterhalogen fluorosulfates according to the general reaction X₂ (XY) + IOSO₂F → IX₂SO₃F (IXYSO₃F); X,Y = I, Br and Cl. When the two compounds IX₂SO₃F and IY₂SO₃F are reacted together according to IX₂SO₃F + IY₂SO₃F → 2 IXYSO₃F; X,Y = I, Br and Cl; ligand redistribution occurs. Infrared and Raman spectra of these compounds are interpreted in terms of ionic structures consisting of the triatomic iodonium (III) cations I₃⁺, IBr₂⁺, ICl₂, IBrCl⁺, I₂Cl⁺ and I₂Br⁺ and the anion SO₃F⁻ with evidence for cation-anion interaction. [the rest of the abstract can be found in the attached PDF file]

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