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OXYFLUORIDES, OXYFLUOROSULPHATES AND OXYCATIONS OF THE HALOGENS AND SELENIUM by HENRY ALBERT CARTER B.Sc. (Hons.) McGill University, Montreal, 1966 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in the Department of CHEMISTRY We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of C k €. VA <-S"f f ^ The University of British Columbia Vancouver 8, Canada Date December /<? . (°170 i ABSTRACT Alternate routes for the preparation of chloryl fluorosulphate, ClO^SO^Fj have been found. Evidence for the existence of the chloronium + cation, C102 , as a red-coloured species in fluorosulphuric acid, HSO^F, has been obtained from electrical conductivity measurements, employing S dichlor 1 C10"2S0 F and (C10"2)2 3°io' y trisulphate, as solutes. nuclear magnetic resonance and uv-visible spectroscopy were also used to study solutions of ClC^SOgF in HSO^F, and are in agreement with the conductivity results. The infrared and Raman spectra of the white solids, chloryl hexafluoroarsenate, chloryl hexafluoroantimonate and dichloryl hexafluorostannate have been obtained. The observed vibrations have been interpreted in terms of ionic compounds where strong cation-anion interaction via fluorine bridging results in a symmetry lowering of the anion. The effect of this interaction is also seen in the Mossbauer spectrum of (ClO^^nF^, where a non-zero quadrupole splitting is found. All compounds dissolve in HSO^F to give red-coloured solutions + as a result of the formation of C1C>2 cations. Tn addition, conductivity measurements show chloryl fluoride, C102F, to be completely'.dissociated + in HSO^F and to form C102 cations and SO^F" anions.', The vibrational spectra of ClF2AsF6, ClF2SbF6 and BrF^bF^ have been recorded. In all compounds, various degrees of anion-cation interaction are found, resulting in the lowering of the symmetry of the anion. In addition, strong coupling of the vibrational modes for BrF„SbF, are observed. ii An alternate route to the preparation of KBrfSO^F)^ was found. A Raman spectrum of this compound indicates a square planar configuration for the anion with polar bromine-oxygen bonds. The Raman spectra obtained for the tris-fluorosulphates ICSO^F)^ and Br(SO^F)^ indicates the presence of two types of fluorosulphates groups and polymeric structures for these compounds. The structure of iodyl fluorosulphate, IC^SO^F, has been examined by Raman spectroscopy and conductivity measurements in HSO^F. Evidence is found for discrete I02 groups linked by covalent bidentate fluorosulphate groups. A Raman spectrum of iodyl fluoride showed it to be dissimilar to the chlorine analogue, CIC^F, and possess a polymeric structure. No discrete I02 groups are found in IO^AsFg on the basis of the infrared spectrum. The new compound selenium (IV) oxyfluorosulphate, SeOCSO^F),,, w t 1 has been prepared by the reaction of $2®^2 -*- ' SeOCl2 or SeO,,. The structure of SeO(S03F)2 has been investigated mainly by Raman spectroscopy and conductimetry in HS03F. A self-dissociation process + of the type,SeOCS03F)2 = SeOCS03F) + S03F~,is suggested for SeO(S03F)2 to explain the results of the physical methods. Also, the addition of SeOCl2 to SeO(S03F)2 results in the formation of SeOCSO_F)C1. Both SeO(SO F)C1 and SeO(SO F) show unusually high Se=0 vibrational stretching frequencies indicating polar Se-0S0„F bonds. iii TABLE OF CONTENTS Page Abstract -'-i Table of Contents iii List of Tables vi List of Figures V11 Acknowledgements ix CHAPTER 1. INTRODUCTION 1.1 Oxyfluorides of the Halogens and Selenium 1 1.2 Scope of the Present Research 4 1.3 Preparative Routes to Fluorosulphates 5 1.4 Preparative Routes to Polyfluoroanion Complexes 7 2. GENERAL EXPERIMENTAL TECHNIQUES 2.1 Vacuum Systems and Apparatus 9 2.2 Reagents 20 2.3 Physical Experimental Methods 21 3. CHLORYL FLUOROSULPHATE: CHLORYL COMPOUNDS (RED) PART I 3.1 Introduction 27 3.2 Experimental 28 3.3 Results and Discussion 37 4. CHLORYL HEXAFLUOROMETALLATES: CHLORYL COMPOUNDS (WHITE) PART II 4.1 Introduction 60 4.2 Experimental 61 4.3 Results and Discussion 62 iv 5. DICHLORYL HEXAFLUOROSTANNATE: CHLORYL COMPOUNDS (WHITE) PART II CONTINUED 5.1 Introduction 79 5.2 Experimental 80 5.3 Results and Discussion 81 6. STRUCTURAL STUDIES OF HEXAFLUOROARSENATES AND -ANTIMONATES OF FLUORO-HALOGEN.HETEROCATIONS 6.1 Introduction 95 6.2 Experimental 99 6.3 Results and Discussion 99 7. BROMYL COMPOUNDS 7.1 Introduction 117 7.2 Experimental 118 7.3 Discussion 119 8. RAMAN STUDIES OF Br(S03F)3, I(S03F)3 AND THE ANIONS Br(S03F)4" AND I(S03F)4~ 8.1 Introduction 122 8.2 Experimental 123 8.3 Discussion 124 9. IODYL COMPOUNDS 9.1 Introduction 134 9.2 Experimental 136 9.3 Results and Discussion 141 10. SELENIUM (IV) OXYFLUOROSULPHATE 10.1 Introduction 160 10.2 Experimental 160 10.3 Results and Discussion 164 V 11. CONCLUSIONS AND SUMMARY 191 REFERENCES 194 APPENDIX 204 vi LIST OF TABLES Page 1. Oxyfluorides of the Halogens and Selenium 2 2. Electrical Conductivity of C102S03F 40 3. First Ionization Potentials of Diatomic and Triatomic Molecules 42 4. Specific Conductivities of ClO^O^, (C102)2S3010 and K S 0 in HS03F 44 C10 S in H S0 49 5. Specific Conductivities of ( 2)2 3°10 2 4 1 6. H NMR Chemical Shifts of Solutions of C102S03F in HS03F 53 7. Electronic Spectra of C102S03F in HSC^F 55 8. The Vibrational Spectra of C10„AsF. and C10„SbF. 63 ZD Z O 9. Assignment of the C102 Vibrations 64 10. C102- Stretching Frequencies 64 11. Assignment of the AsF^ Vibrations 69 12. Assignment of the SbF^ Vibrations 69 13. Specific Conductivities of CIO,,- compounds in HS03F 74 14. Vibrational Frequencies for SnF^~ Compounds 82 15. Vibrational Frequencies for the SnF^ Anion 83 + 16. Vibrational Frequencies of C102 in (ClO^SnFg 89 17. Mossbauer Data for SnF^~ Compounds 93 18. AsFo and SbF^ Complexes of Fluoro- and Oxy-element Heterocations 97 19. The Vibrational Spectra of ClF2SbF6, ClF2AsF6 and BrF„SbF, 100 26 + + 20. Vibrational Frequencies of the species C1F2 and BrF2 106 21. Frequency Assignments of AsF^ in ClF^sF^ 108 22. Fundamental Frequencies for the AsF^ Anion 109 23. Correlation diagram for the >*XEg Species 113 24. Fundamental frequencies for the SbF^ anion 114 25. Vibrational frequencies for the (Hal(S03F)^) Anion 125 26. Vibrational frequencies for Br(S03F)3 and I(S03F)3 126 vii! Page 27. Correlation Diagram for the SO^F group 130 28. Vibrational Spectra of I0F3 and KIO^ 143 29. Vibrational Spectra of I02F, I02AsF6 and 1^ 147 30. Vibrational Frequencies of Bridging SO^F Groups 154 31. Specific Conductivities of I02S03F in HS03F 157 32. Specific Conductivity of Neat SeO(S03F)2 as a Function of Temperature 166 33. Specific Conductivities of SeOCl2 and SeO(S03F)2 in HS03F 171 34. Conductimetric Titration of SeO(S03F)2 in HS03F with Se 175 35. Specific Conductivities of SeO(S03F)2 in Superacid 178 36. The Raman Vibrational Spectra of SeO(S03F)2 and SeO(S03F)Cl 182 37. Raman Spectra of the Solutions: SeOCl2 inlHSC^F, and SeOCl2 in SeO(S03F)2 186 38. Chemical Shifts of some Oxy Selenium-Compounds 187 39. Se-0 and S-0 Stretching Force Constants 189 LIST OF FIGURES 1. Reaction Vessel for Solid-Liquid and Liquid-Liquid Reactions 12 2. Monel Metal 2-part Reaction Vessel (Front View) 13 3. Apparatus for the Preparation of $2®6^2 16 4. Electrical Conductivity Cell 22 5. 3 - Compartment Diaphragm Migration Cell (Front View) 36 6. Conductivities of Fluorosulphates in HS03F 48 7. Conductivity Curve of (CIO )S3010 in H2S04 50 1 8. H NMR Chemical Shifts for Solutions of G,102S03F in HS03F 52 9. Uv-visible Spectrum of C102S03F in HS03F 54 viii 10. The Walsh Diagram for Triatomic Species 56 11. Infrared Spectrum of C102AsF6 65 12. The Raman Spectrum of C102AsF6 66 13. Conductivity Curves of AsF^ Compounds 76 14. The High Resolution Infrared Spectrum of I^SnF^ 85 15. The Infrared Spectrum of (C102)2SnF6 87 16. The Raman Spectrum of (C102)2SnF6 88 17. The Mossbauer Spectrum of (ClO^SnFg 94 18. The Infrared Spectrum of ClF2AsF6 101 19. The Raman Spectrum of ClF^AsF,, 102 ZD 20. The Infrared Spectrum of ClF^SbF, and BrFnSbF^ 103 ZD ZD 21. The Raman Spectra of ClF„SbF^ BrF„SbF. and C10oSbF^ 104 ZD ZD ZD 22. The Crystal Structure of BrF2SbF^ 111 23. The Raman Spectra of KBr(S03F)4, KI(S03F)4 and Br(S03F)3 128 24. Apparatus Used for the Preparation of I0F3 139 25. Raman Spectra of I0F3 and KI02F2 144 26. Raman Spectrum of I02F 148 27. Raman Spectrum of I02S03F 149 28. Infrared Spectra of I0oF and I0„AsF, 150 f- Z ZD 29. The Proposed Structure for I02S03F 156 30. Conductivity Curve of I02S03F in HS03F 158 31. Conductivity of Neat Se0(S03F)2 as a Function of Temperature 167 32. Conductivity Curves of Se0Cl2 and SeO(S03F)2 in HS03F 173 33. Conductimetric Titration of Se0(S03F)2 in HS03F with Se 176 34.

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