DOCSLIB.ORG

Fluorosulfates of Silver, Ruthenium, and Osmium

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Fluorosulfates of Silver, Ruthenium, and Osmium FLUOROSULFATES OF SILVER, RUTHENIUM, AND OSMIUM by PATRICK CHEUNG SHING LEUNG B.Sc. (Hons.), The University of British Columbia, 1975 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA December, 1979 © Patrick Cheung Shing Leung, 1979 In presenting this thesis in partial fulfilment of the requirements f an advanced degree at the University of British Columbia, I agree tha 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 CMMUTtY The University of British Columbia 2075 Wesbrook Place Vancouver, Canada V6T 1W5 ABSTRACT A number of synthetic routes to silver(II) fluorosulfate, Ag(SC>3F)2, were systematically explored. The most suitable and versatile route was found to be the oxidation of silver metal by a solution of bisfluorosulfuryl peroxide, S20gF2, in fluorosulfuric acid, HSO^F, according to: HS03F Ag + S206F2 m- Ag (SC>3F) 2> Additional methods which were found to be suitable involved the oxidation of a wide variety of silver(I) compounds such as S F or the nsert:LOn of S0 Ag20 or AgSO^F by 2°6 2' i- 3 into AgF2. Structural conclusions on Ag(S03F)2 and the other compounds synthesized subsequently were based on the vibrational, elec• tronic and electron spin resonance spectra, as well as on magnetic susceptibility measurements made between 300 and 77 K. Ag(S0.jF)2 was found to be a true compound of divalent silver, 2 + with the Ag ions in either square planar or tetragonally elongated octahedral environment. The only other example of a binary silver(II) compound is AgF2. Several silver(II) fluorosulfate derivatives were prepared and characterized. The reactions of bromine(I) fluorosulfate with metallic silver and other silver(I) substrates resulted in a mixed valence complex Ag^Ag''"'''(SO^F)4 . Its potassium analogue r^AgCSO^F)^, as well as two hexakisfluorosulfato- metallate (IV) complexes AgPtIV (SO..F) , and AgSnIV (SO-.F) . , and 3 b j b the N-donor ligand complex [Agtbipy^l (SO^F^ (i-n which bipy = 2,2'-bipyridine) were also synthesized. The attempt to synthesize a silver(III) fluorosulfato complex by direct insertion of SO^ into CsAgF^ resulted in the fluorination S F and of SC>3, to give 2°6 2 CsAg(S03F)3. Finally, the solvolysi of Ag(S03F)2 in trifluoromethylsulfuric acid, HSO^CF^, allowed its conversion into AgtSO^CF^),,. The principal synthetic route, the oxidation of metal by S2°6F2 s°lur-i°ns in HSO^F, was found to be useful in the preparation of RutSO^F)^. Ruthenium was also found to form a number of anionic derivatives with the metal in the +3 or + + +4 oxidation state, as in M[Ru(SC>3F)4] with M = Cs , C102 ; + + M2[Ru(S03F)6J with M = Cs , K ; and Cs[Ru(S03F)g]. Two different forms of Os(S03F)3 were found. Initial oxidation of osmium metal with S2°gF2 yielded the bright green a-Os(S03F)3, which was converted to the light green 3-form on long standing in S9OfiF;?. - iv - TABLE OF CONTENTS Page ABSTRACT ii LIST OF TABLES xii LIST OF FIGURES xvi ACKNOWLEDGEMENTS xviii I. GENERAL INTRODUCTION 1 A. Introductory Remarks 1 B. The Fluorosulfate Radical And Its Anion.... 6 C. Synthetic Routes To Fluorosulfates 19 D. Vibrational Studies Of The Fluorosulfate Group 2 5 E. Transition Metal Fluorosulf ates 30 F. Structural Characterizations Of Transition Metal Fluorosulf ates 34 II. - EXPERIMENTAL 35 A. Apparatus 35 1. Pyrex vacuum line 35 2. Metal vacuum line. 36 3. Reactions vessels 37 4. HSO-jF distillation apparatus 44 5. HSO^CF^ distillation apparatus 44 6. Drybox 4 6 - v - Page 7. Miscellaneous 46 B. Instrumental Methods 47 1. -Infrared spectroscopy 47 2. Raman spectroscopy 50 3. Visible and ultraviolet spectroscopy.... 50 4. Magnetochemistry 51 5. Electron spin resonance spectroscopy.... 53 6. Mossbauer spectroscopy 53 7. Melting points 54 C. Chemicals 54 1. Commercial sources 54 2. Preparative reactions 57 D. Chemical Analyses 61 1. Elemental analyses 61 2. Oxidation states determinations 6 3 III. FLUOROSULFATES OF SILVER(II) 64 A. Introduction 64 B. Silver (II) Fluorosulfate 76 1. Introduction 76 2. Synthetic reactions 77 (a) Reactions with fluorosulfuryl peroxide 77 (b) Reactions with mixtures of HSO^ and S2°6F284 - vi - Page (c) The reaction of silver(II) fluoride and sulfur trioxide 85 (d) Reactions with bromine monofluoro- sulfate 86 (e) Discussion 88 3. Characterization of Ag(S03F)2 96 (a) Infrared spectra 96 (b) Electronic spectra 99 (c) Magnetic susceptibility measurements 104 (d) Electron spin resonance spectra Ill (e) Oxidation state determination 117 (f) Thermal decomposition 118 C. Coordination Complex Of Ag(S03F)2, [Ag(bipy)2] (S03F)2 119 1. Introduction 119 2. Synthesis of silver(II) bis(2,2'-bipy- ridyl) bis (fluorosulfate) 120 3. Characterizations 121 (a) Vibrational spectra 121 (b) Electronic spectra 126 (c) Magnetic susceptibility 128 (d) E.S.R. spectra 130 D. Anionic Fluorosulfato Complexes Of Silver(II) 132 1. Introduction 132 - vii - Page 2. Syntheses and elemental analyses 132 (a) Ag3(S03F)4 . 132 (b) K2[Ag(S03F)4] 132 3. Experimental results and discussions.... 135 (a) Infrared spectra 135 (b) Magnetic susceptibility measurements 135 (c) E.S.R. spectra 145 (d) Oxidation state determination and thermal decomposition of Ag3(S03F)4. 147 E. Silver(II) Hexakis(fluorosulfato)metallate(IV) 148 1. Introduction 148 2. Syntheses and elemental analyses 149 (a) AgPt(S03F)6 149 (b) AgSn(S03F)6 150 3. Characterizations 151 (a) Vibrational spectra . 151 (b) Electronic spectra 154 (c) Magnetic susceptibility measurements 156 (d) E.S.R. spectra 160 119 (e) Sn Mossbauer spectra of AgSn(S03F)g 162 F. Reactions Of Ag(S03F)2 164 1. Reaction of Ag(S03F)2 with elemental fluorine 164 - viii - Page (a) Introduction 164 (b) Conversion of Ag(S03F)2 into AgF2«.. 165 (c) Discussion 166 2. Reactions with some other halogens 167 (a) Chlorine 167 (b) Bromine 167 3. Reactions with chloryl fluorosulfate.... 169 4. Reaction with pyridine 171 5. Reaction with acetonitrile 172 6. Reaction with antimony pentafluoride.... 173 G. Attempts to obtain higher oxidation states of silver 175 S F 175 1. The reaction of AgO and 2°6 2 2. The reaction of CsAgF4 and S03 176 (a) Introduction 176 (b) Synthetic reactions 177 (c) Characterization of CsAg(S03F)3 179 IV. SILVER (II) TRIFLUOROMETHYLSULFATE 18 6 A. Introduction 18 6 B. Synthetic Reactions 188 1. Synthesis of silver(II) trifluoromethyl- sulfate 188 (a) Reaction of Ag(SO-jF)0 and HSO^CF-,... 188 - ix - Page (b) Other synthetic attempts 189 (c) Discussion 190 2. Conversion of Ag(S03CF3)2 into [Ag(bipy)2] (S03CF3)2 193 C. Experimental Result And Discussion 193 1. Infrared spectrum 193 2. Magnetic measurements 194 3. E.S.R. spectrum 198 4. Thermal decomposition 200 D. Conclusion 202 V. FLUOROSULFATES OF RUTHENIUM 203 A. Introduction 203 B. Ruthenium (III) Fluorosulfate 207 1. Preparation and elemental analysis 2 07 2. Experimental result and discussion .... 208 (a) Infrared spectra 208 (b) Magnetic susceptibilities 210 (c) Electronic spectra 213 (d) E.S.R. spectra 217 (e) Discussion 219 C. Anionic Fluorosulfato Complexes Of Ruthenium (III) 222 - x - Page 1. Introduction 222 2. Syntheses and elemental analyses 222 (a) Cl02[Ru(S03F)4] 222 (b) Cs[Ru(S03F)4] 223 (c) The attempted synthesis of Cs3 [Ru(S03F) ] 223 3. Characterizations 224 (a) Infrared spectra 224 (b) Magnetic susceptibilities 227 (c) E.S.R. spectra 227 D. Anionic Fluorosulfato Complexes of Ruthenium(IV) 229 1. Introduction 229 2. Preparations and elemental analyses 2 31 (a) K2 [Ru(S03F) ] 231 (b) Cs2 [Ru(S03F) ] 231 (c) Cs [Ru(S03F) ] 232 3. Characterizations 232 (a) Vibrational spectra 232 (b) Magnetic susceptibility measurements 233 (c) Electronic spectra 237 E. Other Synthetic Attempts 239 l.i. Reaction of S20gF2 with ruthenium metal. 239 2. Reaction of So0_F_ with Ru(SO_,F)_ 240 2 6 2 3 3 3. Reaction of BrS0oF with ruthenium metal. 24 0 - xi - Page 4. Reactions of Ru02 241 VI. OSMIUM (III) FLUOROSULFATE 242 A. Introduction 242 B. Synthetic Reactions And Elemental Analyses 1. Synthesis of Os (S03F) 245 2. Other synthetic attempts 246 3. Attempts to synthesize fluorosulfato complexes of osmium 247 C. Experimental Result And Discussion 248 1. Vibrational spectra 248 2. Magnetic susceptibility measurements.... 250 3. Electronic spectra 253 4. E.S.R. spectra 255 5. Conclusion 256 VII. GENERAL CONCLUSION 257 A. Summary 25 7 B. Suggestions For Further Work 258 BIBLIOGRAPHY 260 APPENDICES 277 - xii - LIST OF TABLES Table Page 1. Fundamental Frequencies Of Matrix Isoated SO-jF and Comparison With Other Results 9 2. Ligand Field Parameters For Some Nickel Salts... 16 3. Selected Parameters For F~ And S03F~ 18 S F and 4. Some Physical Properties Of HS03F, 2°6 2 BrS03F 24 5. Structural Bonding Differentiation For The S03F Group 2 6 6. Commercially Available Types Of Apparatus 48 7. Chemicals 55 8. Some Ionization Potentials Of Silver And Copper. 65 9. Synthetic Routes To Ag(S03F)2 92 10. Infrared Spectra Of Ag(S03F)2 And Related Compounds 98 11. Electronic Spectra Of Ag(S03F)2 And Related Compounds 102 12. Magnetic Susceptibilities And Magnetic Moments Of Ag (S03F) 106 13.
Load more

Recommended publications
  • (VI) and Chromium (V) Oxide Fluorides
    Portland State University PDXScholar Dissertations and Theses Dissertations and Theses 1976 The chemistry of chromium (VI) and chromium (V) oxide fluorides Patrick Jay Green Portland State University Follow this and additional works at: https://pdxscholar.library.pdx.edu/open_access_etds Part of the Chemistry Commons Let us know how access to this document benefits ou.y Recommended Citation Green, Patrick Jay, "The chemistry of chromium (VI) and chromium (V) oxide fluorides" (1976). Dissertations and Theses. Paper 4039. https://doi.org/10.15760/etd.5923 This Thesis is brought to you for free and open access. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of PDXScholar. Please contact us if we can make this document more accessible: [email protected]. All ABSTRACT OF THE TllESIS OF Patrick Jay Green for the Master of Science in Chemistry presented April 16, 1976. Title: Chemistry of Chromium(VI) and Chromium(V) Oxide Fluorides. APPROVEO BY MEMBERS OF THE THESIS CO'"o\l TIEE: y . • Ii . ' I : • • • • • New preparative routes to chromyl fluoride were sought. It was found that chlorine ironofluoride reacts with chromium trioxide and chromyl chlo­ ride to produce chromyl fluoride. Attempts were ~ade to define a mechan­ ism for the reaction of ClF and Cr0 in light of by-products observed 3 and previous investigations. Carbonyl fluoride and chromium trioxide react to fom chro·yl fluoride and carbo:i dioxide. A mechanism was also proposed for this react10n. Chromium trioxide 11itl\ l~F6 or WF5 reacts to produce chromyl fluoride and the respective oxide tetrafluoride. 2 Sulfur hexafluoride did not react with Cr03.
    [Show full text]
  • Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 13
    This PDF is available from The National Academies Press at http://www.nap.edu/catalog.php?record_id=15852 Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 13 ISBN Committee on Acute Exposure Guideline Levels; Committee on 978-0-309-29025-8 Toxicology; Board on Environmental Studies and Toxicology; Division on Earth and Life Studies; National Research Council 292 pages 6 x 9 PAPERBACK (2013) Visit the National Academies Press online and register for... Instant access to free PDF downloads of titles from the NATIONAL ACADEMY OF SCIENCES NATIONAL ACADEMY OF ENGINEERING INSTITUTE OF MEDICINE NATIONAL RESEARCH COUNCIL 10% off print titles Custom notification of new releases in your field of interest Special offers and discounts Distribution, posting, or copying of this PDF is strictly prohibited without written permission of the National Academies Press. Unless otherwise indicated, all materials in this PDF are copyrighted by the National Academy of Sciences. Request reprint permission for this book Copyright © National Academy of Sciences. All rights reserved. Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 13 Committee on Acute Exposure Guideline Levels Committee on Toxicology Board on Environmental Studies and Toxicology Division on Earth and Life Studies Copyright © National Academy of Sciences. All rights reserved. Acute Exposure Guideline Levels for Selected Airborne Chemicals: Volume 13 THE NATIONAL ACADEMIES PRESS 500 FIFTH STREET, NW WASHINGTON, DC 20001 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Insti- tute of Medicine.
    [Show full text]
  • Toxicological Profile for Chlorine Dioxide and Chlorite
    TOXICOLOGICAL PROFILE FOR CHLORINE DIOXIDE AND CHLORITE U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service Agency for Toxic Substances and Disease Registry September 2004 CHLORINE DIOXIDE AND CHLORITE ii DISCLAIMER The use of company or product name(s) is for identification only and does not imply endorsement by the Agency for Toxic Substances and Disease Registry. CHLORINE DIOXIDE AND CHLORITE iii UPDATE STATEMENT Toxicological Profile for Chlorine Dioxide and Chlorite, Draft for Public Comment was released in September 2002. This edition supersedes any previously released draft or final profile. Toxicological profiles are revised and republished as necessary. For information regarding the update status of previously released profiles, contact ATSDR at: Agency for Toxic Substances and Disease Registry Division of Toxicology/Toxicology Information Branch 1600 Clifton Road NE, Mailstop F-32 Atlanta, Georgia 30333 CHLORINE DIOXIDE AND CHLORITE vi *Legislative Background The toxicological profiles are developed in response to the Superfund Amendments and Reauthorization Act (SARA) of 1986 (Public law 99-499) which amended the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA or Superfund). This public law directed ATSDR to prepare toxicological profiles for hazardous substances most commonly found at facilities on the CERCLA National Priorities List and that pose the most significant potential threat to human health, as determined by ATSDR and the EPA. The availability of the revised priority list of 275 hazardous substances was announced in the Federal Register on November 17, 1997 (62 FR 61332). For prior versions of the list of substances, see Federal Register notices dated April 29, 1996 (61 FR 18744); April 17, 1987 (52 FR 12866); October 20, 1988 (53 FR 41280); October 26, 1989 (54 FR 43619); October 17, 1990 (55 FR 42067); October 17, 1991 (56 FR 52166); October 28, 1992 (57 FR 48801); and February 28, 1994 (59 FR 9486).
    [Show full text]
  • Healthcare Sterilisation: Challenging Practices, Volume 2
    Healthcare Volume 2 Volume Healthcare Sterilisation: Published by Smithers Rapra Technology Ltd, 2014 Challenging Practices Sterilisation: Volume 2 The collection of topics in this second volume of the book reflects challenges the reader to Challenging think beyond standard methods and question why certain current procedures remain static while technological advances abound in other aspects of sterilisation technology. By small means, better practices may come to pass to help answer some of the residual healthcare sterilisation and nosocomial infection queries: • What are some of the current challenges in healthcare sterilisation, and how can they be handled? • What are some of the acceptable current non-traditional sterilisation methods, challenging alternatives, and novel modalities? • What are some of the packaging, validation and statistical considerations of sterilisation Wayne J. Rogers practices? • How does design-of-product and packaging interrelate with sterilisation processing? Practices • Are the current sterility media and practices optimal for recovery of more modified and more resistant viable organism entities and product? • Are there increased sterility and product quality needs with new types of implantables and technological advances within the three dimensional combinations of diagnostics, drug release and challenging medical devices? Wayne J. Rogers Wayne Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 Web: www.polymer-books.com Healthcare Sterilisation: Challenging Practices Volume 2 Wayne J. Rogers A Smithers Group Company Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.polymer-books.com First Published in 2014 by Smithers Rapra Technology Ltd Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK ©Smithers Information Ltd., 2014 All rights reserved.
    [Show full text]
  • Molecular Structures of Gas-Phase Polyatomic Molecules Determined by Spectroscopic Methods
    Molecular Structures of Gas-Phase Polyatomic Molecules Determined by Spectroscopic Methods Marlin D. Harmony Department of Cherni..str)', The University of Kansas, Lawrence, KS 66045 Victor W. Laurie Department of Chemistry, Princeton Unit'er.it)", Princeton, NJ 08540 Robert L. Kuczkowski Department of Chemistry, University of Michigan, Ann Arbor, Ml48109 R. H. Schwendeman Department of Chemistry, Michigan State University, East Lansing, MI 48824 D. A. Ramsay Her::;berg institute of Astrophysics, National Research COl/neil of Canada, OIlf1l<'U, KIA ORG, Canada Frank J. Lovas, Walter J. Lafferty, and Arthur G. Maki National Bureau of Standards, Washing/Oil, DC 20334 Spectroscopic data related to the structures of polyatomic molecules in the gas phase have been reviewed, critically evaluated, and compiled. All reported bond distances and angles have been classified as equilibrium (r 0)' average (r,), substitution (r.), or effective (ro) parameters, and have been given a quality rating which is a measure of the parameter uncertainty. The surveyed literature includes work from all of the areas of gas-phase spectroscopy from which precise quantitative struc· tural information can be derived. Introductory material includes definitions of the various types of parameters and a description of the evaluation procedure. Key words: Bond angles; bond distances; gas·phase polyatomic molecules; gas·phase spectroscopy; microwave spectroscopy; molecular conformation; molecular spectroscopy; molecular structure; molecules; SLrUClure. Contents Page Page 1. Introduction.... .. ............. 619 Inorganic Molecules ....................... 628 2. Definitions of Structural Parameters ......... 620 C1 Molecules ............................. 650 3. Uncertainties ............................ 623 C~ Molecules ............................. 668 4,. Evaluation Procedure ..................... 625 C3 Molecules ............................. 688 5. Description of Tables ..................... 625 c.! Molecules ............................. 702 Appendix: Selected Diatomic Molecule Distances .
    [Show full text]
  • Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005)
    NOMENCLATURE OF INORGANIC CHEMISTRY IUPAC Recommendations 2005 IUPAC Periodic Table of the Elements 118 1 2 21314151617 H He 3 4 5 6 7 8 9 10 Li Be B C N O F Ne 11 12 13 14 15 16 17 18 3456 78910 11 12 Na Mg Al Si P S Cl Ar 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 55 56 * 57− 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba lanthanoids Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 87 88 ‡ 89− 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 Fr Ra actinoids Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo * 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ‡ 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr International Union of Pure and Applied Chemistry Nomenclature of Inorganic Chemistry IUPAC RECOMMENDATIONS 2005 Issued by the Division of Chemical Nomenclature and Structure Representation in collaboration with the Division of Inorganic Chemistry Prepared for publication by Neil G.
    [Show full text]
  • I&A-Red Absorption Spectrum of Gaseous Chloryl Fluoride
    Spectrochimica Acta, 1963, Vol. 19, pp. 1449 to 1466. Pergamon Press Ltd. Printed in Northern Ireland I&a-red absorption spectrum of gaseous chloryl fluoride (FClO, ) A. J. ARV~A and P. J. AYMONINO Instituto Superior de Inve&igaciones. Facultad do Quimica y Farmacia. Universidad National do La Plat’a. La Plata. Argentina (Received 12 Decenzber 1962) Abstract-The infrared spectrum of gaseous chloryl fluoride has been investigated in the region bet,ween 2.5 and 25 p at pressures from ca. 1 mm Hg to ca. 1 atm at room temperature. The strong bands located at 1265, 1104, 627 and 542 cm-l have been assigned to four of the six fundamental vibrations expected for a pyramidal tctratomic molecule pertaining to the C, point group. The other two bands could not be detected but they were tcnt,atively located at 405 and 349 cm-l. A correlation of the chloryl fluoride spectrum with spectra of related molecules and ions has been useful to the assignment of the bands. Chloryl fluoride was obtained by SCHIV~TZand SCHUMACHER[I] in the thermal reaction between fluorine and chlorine dioxide. Its infrared absorption spectrum in the sodium chloride region at low gas pressure has been published by SMITH et aZ. [2], although BURKE and SNITH had reported in 1956, at the Columbus Sym- posium of Molecular Structure and Spectra, that two weak bands which were observed by CLAASSEN et al. [3] in the infrared absorption spectrum of impure chlorine trifiuoride, were due to the presence of chloryl fluoride. SMITH et al. obtained the spectrum for analytical purposes employing a lo-cm path length cell and silver chloride windows.
    [Show full text]
  • (Hons.) Mcgill University, Montreal, 1966
    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.
    [Show full text]
  • FLUOROSULFATE DERIVATIVES of NIOBIUM and TANTALUM and THEIR BEHAVIOR AS COMPONENTS of NOVEL SUPERACID SYSTEMS by WALTER VLADIMIR
    FLUOROSULFATE DERIVATIVES OF NIOBIUM AND TANTALUM AND THEIR BEHAVIOR AS COMPONENTS OF NOVEL SUPERACID SYSTEMS By WALTER VLADIMIR CICHA B.Sc, The University of British Columbia, 1984 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA August, 1989 © Walter Vladimir Cicha, 1989 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 or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia Vancouver, Canada DE-6 (2/88) ii ABSTRACT The goal of this study was to develop new superacid systems based on fluorosulfuric acid, HSO3F, (the strongest monoprotonic BrOnsted acid) and metal fluorosulfates capable of acting as Lewis acids. The in situ oxidation of niobium and tantalum in HSO3F by bis(fluorosulfuryl) peroxide, S2O6F2. resulted in the formation of the highly solvated Lewis acids M(S03F)5 with M = Nb or Ta. Based on electrical conductivity measurements, both solutes were found to behave as moderately strong, monoprotonic acids in HSO3F, with Ta(SC>3F)5 the markedly stronger acid of the two.
    [Show full text]
  • CLASS 1 No. 1AGO
    A SPECTROSCOPIC AND THERMODYNAMIC INVESTIGATION OF SOME IODINE OXYGEN FLUORirŒ COMPOUNDS A thesis submitted by MICHAEL ARTHUR JENKINSON in candidature for the degree of Doctor of Philosophy of the University of London October, 1972 Royal Holloway College, Englefield Green, Surrey. CLASS 1 No. 1 AGO. No. jl Tt ACQ i r f & ProQuest Number: 10096776 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10096776 Published by ProQuest LLC(2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. Microform Edition © ProQuest LLC. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Abstract The solid-state infrared and Raman spectra of the dioxodifluoroiodate salts, (M = Na, K, Rb and NH^), iodyl fluoride, lO^F, and the Raman spectrum of iodine oxide trifluoride, lOF^ are reported. Assignmentiof the vibrational frequencies of the lO^F^ ion and lOF^ have been made and approximate stretching force constants calculated. Shifts in the positions of the stretching modes of MIO^F^ with changing cation are discussed. The vibrational spectrum of iodyl fluoride indicates the presence of a polymeric structure and various possible arrangements are suggested. The synthesis of complexes involving the iodyl ion, / lOg*, have been attempted, Calorimetric measurements, in the isoperibol mode, of the enthalpies of hydrolysis of the dioxodifluoroiodate salts, iodine oxide trifluoride, iodyl fluoride, iodine pentafluoride and -hexafluoroiodate compounds, MIF^ (M = K, Rb, Cs) are reported.
    [Show full text]
  • Naming and Indexing of Chemical Substances for Chemical Abstractstm
    Naming and Indexing of Chemical Substances for Chemical AbstractsTM 2007 Edition A publication of Chemical Abstracts Service Published by the American Chemical Society Naming and Indexing of Chemical Substances for Chemical AbstractsTM A publication of Chemical Abstracts Service Published by the American Chemical Society Copyright © 2008 American Chemical Society All Rights Reserved. Printed in the USA Inquiries concerning editorial content should be sent to: Editorial Office, Chemical Abstracts Service, 2540 Olentangy River Road, P.O. Box 3012, Columbus, Ohio 43210-0012 USA SUBSCRIPTION INFORMATION Questions about CAS products and services should be directed to: United States and Canada: CAS Customer Care Phone: 800-753-4227 (North America) 2540 Olentangy River Road 614-447-3700 (worldwide) P.O. Box 3012 Fax: 614-447-3751 Columbus, Ohio 43210-0012 USA E-mail: [email protected] Japan: JAICI (Japan Association for International Phone: 81-3-5978-3621 Chemical Information) Fax: 81-3-5978-3600 6-25-4 Honkomagome E-mail: [email protected] Bunkyo-ku, Tokyo Japan, 113-0021 Countries not named above: Contact CAS Customer Care, 2540 Olentangy River Road, P.O. Box 3012, Columbus, Ohio 43210-0012 USA; Telephone 614-447-3700; Fax 614-447-3751; E-mail [email protected]. For a list of toll-free numbers from outside North America, visit www.cas.org. 1 Naming and Indexing of Chemical Substances for Chemical Abstracts 2007 ¶ 102 NAMING AND INDEXING OF CHEMICAL SUBSTANCES 101. Foreword. Although the account which follows describes in consid- zwitterions (inner salts, sydnones). The changes for the Fourteenth (1997- erable detail the selection of substance names for Chemical Abstracts (CA) in- 2001) Collective Index period affect coordination nomenclature, stereochemi- dexes, it is not a nomenclature manual.
    [Show full text]