Inorganic Reactions and Methods V 3 – The of Bonds to Halogens Pt 1

For the first time, the discipline of modern inorganic chemistry has been systematized according to a plan constructed by a council of editorial advisors and consultants, among them are three Nobel laureates (E.O. Fischer, H. Taube and G. Wilkinson). Rather than producing a collection of unrelated review articles, the series creates a framework which reflects the creative potential of this scientific discipline. Thus, it stimulates future development by identifiying areas which are fruitful for further research. The work is indexed in a unique way by a structured system which maximizes its usefulness to the reader. It augments the organization of the work by providing additional routes of access for specific compounds, reactions and other topics.

Table of Contents:
How to Use this Book Preface to the Series Editorial Consultants to the Series Contributors to Volume 3 2. Formation of Bonds to Halogens (Part 1) 2.1. Introduction 2.2. Formation of Halogen Halogen Bonds 2.2.1. Introduction 2.2.2. Preparation of the Elemental Halogens 2.2.2.1. by Anodic Oxidation 2.2.2.1.1. of Fluoride Ion. 2.2.2.1.2. of Chloride Ion. 2.2.2.1.3. of Bromide Ion. 2.2.2.1.4. of Iodide Ion. 2.2.2.2. by Chemical Oxidation 2.2.2.2.1. of Fluoride. 2.2.2.2.2. of Chloride. 2.2.2.2.3. of Bromide. 2.2.2.2.4. of Iodide. 2.2.2.3. by Reduction. 2.2.2.4. by Dissociation of Halides. 2.2.2.5. Diastatine Synthesis. 2.2.3. Preparation of Cationic Polyhalogens (Homonuclear and Heteronuclear) 2.2.3.1. by Halide Anion Transfer in Acid - Base Reactions. 2.2.3.2. by Oxidation of Elemental Halogens or Interhalogens. 2.2.4. Preparation of Neutral Interhalogens 2.2. Formation of Halogen Halogen Bonds 2.2.4.1. from the Elements. 2.2.4.1.1. by Fluorination of Cl2, Br2 and I2. 2.2.4.1.2. by Chlorination of Br2 and I2. 2.2.4.1.3. by Bromination of I2. 2.2.4.2. from the Oxidation of Anionic Halides. 2.2.4.3. from the Oxidation of Organoiodides 2.2.4.3.1. by F2 or Cl2. 2.2.4.3.2. by Oxidizing Fluorinating Agents (Excluding F2). 2.2.4.4. Preparation of Neutral and Cationic Interhalogen Compounds Containing Astatine 2.2.5. Preparation of Aryliodo Fluorides from Aryliodo Oxides 2.2.5.1. from Aryliodoso and Aryliodo Compounds and HF. 2.2.5.2. from Aryliodo Compounds and SF4. 2.2.5.3. by Electrochemical Fluorination of Aryliodo Compounds. 2.2.5.4. from Aryliodo Compounds and XeF2. 2.2.5.5. from Aryliodo Compounds and F2. 2.2.6. Preparation of Anionic Polyhalides (Homonuclear and Heteronuclear) 2.2.6.1. from Elemental Halogens with Halide Anion. 2.2.6.2. from Interhalogen Compounds with Halide Anion. 2.2.6.3. Preparation of Anionic Polyhalides Containing Astatine. 2.2.7. Preparation of Halogen Oxyfluorldes 2.2.7.1. from Halogen Oxides with F2. 2.2.7.2. from Halogen Oxides with Fluorinating Agents Other than F2. 2.2.7.3. from Halogen Oxyfluorides with Fluorinating Agents. 2.2.7.4. by Disproportionation of Halogen Oxyfluorides. 2.2.7.5. from Positive Halogen Compounds with Fluorinating Agents. 2.2.7.6. from Halogen Oxyacids and Their Salts with Fluorinating Agents. 2.2.7.7. by Elimination. 2.3. Formation of Bonds between Halogens and Group VB (O, S, Se, Te, Po) Elements 2.3.1. Introduction 2.3.2. from the Elements 2.3.2.1. from Halogenation by Elemental Halogens 2.3.2.1.1. to Give the Oxygen - Halogen Bond. 2.3.2.1.2. to Give the Sulfur - Halogen Bond. 2.3.2.1.3. to Give the Se - Halogen Bond. 2.3.2.1.4. to Give the Te - Halogen Bond. 2.3.2.1.5. to Give the Po - Halogen Bond. 2.3.2.2. from Halogenation by Hydrogen Halides. 2.3.2.3. from Halogenation by Oxidizing Halides 2.3.2.3.1. to give the Oxygen - Halogen Bond. 2.3.2.3.2. to Give the Sulfur - Halogen Bond. 2.3.2.3.3. to Give the Se - Halogen Bond. 2.3.2.3.4. to Give the Te - Halogen Bond. 2.3.2.4. from Halogenation by Organic Halides. 2.3.2.5. from Oxidation of Elemental Halogens by Ozone. 2.3.3. from Cleavage of the Group VIB - Hydrogen Bond (Excluding Polonium) 2.3.3.1. by Halogens 2.3.3.2. by Oxidizing Halides. 2.3.4. from Cleavage of the Group VIB - Carbon bond 2.3.4.1. by Halogens. 2.3.4.2. by Oxidizing Halides or Electrochemical Fluorination. 2.3.5. from Cleavage of the Group VIB Group IVB Element Bond 2.3.5.1. by Halogens. 2.3.5.2. by Oxidizing Halides. 2.3.6. from Cleavage of the Group VIB - Oxygen Bond 2.3.6.1. by Halogens. 2.3.6.1.1. to Give the Sulfur - Halogen Bond. 2.3.6.1.2. to Give the Se - Halogen Bond. 2.3.6.1.3. to Give the Te - Halogen Bond. 2.3.6.2. by Hydrogen Halides 2.3. Formation of Bonds between Halogens and Group VB (O, S, Se, Te, Po) Elements 2.3.6.2.1. to Give the Sulfur - Halogen Bond. 2.3.6.2.2. to Give the Si - Halogen Bond. 2.3.6.2.3. to Give the Te - Halogen Bond. 2.3.6.2.4. to Give the Po - Halogen Bond. 2.3.6.3. by Organic Halides 2.3.6.3.1. to Give the Sulfur - Halogen Bond. 2.3.6.3.2. to Give the Se - Halogen Bond. 2.3.6.3.3. to Give the Te - and Po - Halogen Bond. 2.3.6.4. by Metal Halides 2.3.6.4.1. to Give the Sulfur - Halogen Bond. 2.3.6.4.2. to Give the Se - Halogen Bond. 2.3.6.4.3. to Give the Te - Halogen Bond. 2.3.6.5. by Nonmetal Halides 2.3.6.5.1. to Give the Sulfur Halogen Bond. 2.3.6.5.2. to Give the Se - Halogen Bond. 2.3.6.5.3. to Give the Te - Halogen and Po - Halogen Bond. 2.3.7. by Halogenation of Group VIB Oxides and Oxoanions 2.3.7.1. with Elemental Halogens 2.3.7.1.1. to Give the Sulfur - Halogen Bond. 2.3.7.1.2. to Give the Se - , Te - , Po - Halogen Bond. 2.3.7.2. with Halogen Halides 2.3.7.2.1. to Give the Sulfur - Halogen Bond. 2.3.7.2.2. to Give the Se - , Te - , Po - Halogen Bond. 2.3.7.3. with Nonmetal Halides 2.3.7.3.1. to Give the Sulfur - Halogen Bond. 2.3.7.3.2. to Give the Se - and Te - Halogen Bonds. 2.3.7.4. with Metal Halides 2.3.7.4.1. to Give the Sulfur - Halogen Bond. 2.3.7.4.2. to Give Se - and Te - Halogen Bond. 2.3.8. from Cleavage of the Group VIB - Group VIB Element Bond 2.3.8.1. by Elemental Halogens 2.3.8.1.1. to Give the Oxygen - Halogen Bond. 2.3.8.1.2. to Give the Sulfur - Halogen Bond. 2.3.8.1.3. to Give the Se - and Te - Halogen Bond. 2.3.8.2. by Hydrogen Halides. 2.3.8.3. from Cleavage of the Group VIB - Element Bond by Other Halides 2.3.8.3.1. to Give the Oxygen - Halogen Bond. 2.3.8.3.2. to Give the Sulfur - Halogen Bond. 2.3.8.3.3. to Give the Se - Halogen Bond. 2.3.8.3.4. to Give the Te - Halogen Bond. 2.3.9. from Cleavage of the Group VIB - Nitrogen Bond 2.3.9.1. by Halogens 2.3.9.2. by Hydrogen Halides. 2.3.9.3. by Other Halides. 2.3.10. from Cleavage of the Group VlB - Group VB Bonds 2.3.10.1. by Halogens. 2.3.10.2. by Hydrogen Halides 2.3.10.3. by Other Halides 2.3.11. from Further Oxidative Addition of Low Oxidation State Group VIB Compounds 2.3.11.1. with Elemental Halogens 2.3.11.1.1. to Give the Sulfur - Halogen Bond. 2.3.11.1.2. to Give the Se - Halogen Bond. 2.3.11.1.3. to Give the Te - and Po - Halogen Bond. 2.3.11.2. with Hydrogen Halides. 2.3.11.3. with Nonmetal Halides 2.3.11.3.1. to Give the Sulfur - Halogen Bond. 2.3.11.3.2. to Give the Se - Halogen Bond. 2.3.11.3.3. the Te - and Po - Halogen Bonds. 2.3.11.4. with Metal Halides 2.3.11.4.1. to Give the Sulfur - Halogen Bond. 2.3.11.4.2. to Give the Se - , Te - and Po - Halogen Bond. 2.3.11.5. with Organic Halides. 2.3.12. from Metathetical Reactions (Halogen - Halogen Exchange) 2.3.12.1. by Halogenation with Metal Halides 2.3.12.1.1. to Give the Oxygen - Halogen Bond. 2.3.12.1.2. to Give the Sulfur - Halogen Bond. 2.3.12.1.3. to Give the Se - Halogen Bond. 2.3.12.1.4. to Give the Te - Halogen Bond. 2.3. Formation of Bonds between Halogens and Group VB (O, S, Se, Te, Po) Elements 2.3.12.2. by Halogenation with Nonmetal Halides 2.3.12.2.1. to Give the Oxygen - Halogen Bond. 2.3.12.2.2. to Give the Sulfur - Halogen Bond. 2.3.12.2.3. to Give the Se - Halogen Bond. 2.3.12.2.4. to Give the Te - Halogen Bond. 2.3.13. Preparation of Astatine - Group VIB Element Bonds 2.3.13.1. Preparation of Astatine - Oxygen Bonds. 2.3.13.2. Other Astatine - Group VIB Element Bonds. 2.4. Formation of Bonds between Halogens and Group VB (N, P, As, Sb, Bi) Elements 2.4.1. Introduction 2.4.2. from the Elements 2.4.2.1. to Give Group VB Fluorides. 2.4.2.2. to Give Group VB Chlorides. 2.4.2.3. to Give Group VB Bromides. 2.4.2.4. to Give Group VB Iodides. 2.4.3. from Halogenation of Group VB Elements 2.4.3.1. by Hydrogen Fluoride To Give Group VB Fluorides. 2.4.3.2. by Other Inorganic Halides to Give Group VB Halides 2.4.3.2.1. from Group IIIB Halides. 2.4.3.2.2. from Group IVB Halides. 2.4.3.2.3. from Group VB Halides. 2.4.3.2.4. from Group VIB Halides. 2.4.3.2.5. from Group VIIB Halides. 2.4.3.3. by Organic Halides to Give Group VB Halides 2.4.3.3.1. from Alkyl Halides. 2.4.3.3.2. from Aryl Halides. 2.4.4. from Cleavage of the Group VB - Hydrogen Bond 2.4.4.1. by Halogens 2.4.4.1.1. to Give Group VB Fluorides. 2.4.4.1.2. to Give Group VB Chlorides. 2.4.4.1.3. to Give Group VB Bromides. 2.4.4.1.4. to Give Group VB Iodides. 2.4.4.2. by Other Halides 2.4.4.2.1. to Give Group VB Halides from Hypohalites. 2.4.4.2.2. to Give Group VB Halides from Hydrogen Halides. 2.4.4.2.3. to Give Group VB Halides from Group IIIB Halides. 2.4.4.2.4. to Give Group VB Halides from Group IVB Halides. 2.4.4.2.5. to Give Group VB Halides from Group VB Halides. 2.4.4.2.6. to Give Group VB Halides from Group VIB Halides. 2.4.4.2.7. to Give Group VB Halides from Group VIIB Halides. 2.4.4.2.8. to Give Group VB Halides from Transition Metal Halides. 2.4.5. from Cleavage of the Group VB Carbon Bond 2.4.5.1. by Halogens 2.4.5.1.1. to Give Group VB Fluorides. 2.4.5.1.2. to Give Group VB Chlorides. 2.4.5.1.3. to Give Group VB Bromides. 2.4.5.1.4. to Give Group VB Iodides. 2.4.5.2. by Hydrogen Halides 2.4.5.2.1. to Give Group VB Fluorides. 2.4.5.2.2. to Give Group VB Chlorides. 2.4.5.2.3. to Give Group VB Bromides. 2.4.5.2.4. to Give Group VB Iodides. 2.4.5.3. by Other Inorganic Halides 2.4.5.3.1. of Group IIIB. 2.4.5.3.2. of Group IVB. 2.4.5.3.3. of Group VB. 2.4.5.3.4. of Group VIB. 2.4.5.3.5. of Group VIIB. 2.4.5.3.6. of Transition Metal Halides. 2.4.5.4. by Organic Halides. 2.4.6. from Cleavage of the Group VB - Other Group IVB Element Bond 2.4.6.1. by Halogens 2.4.6.1.1. to Give Nitrogen Halides. 2.4. Formation of Bonds between Halogens and Group VB (N, P, As, Sb, Bi) Elements 2.4.6.1.2. to Give Phosphorus Halides. 2.4.6.1.3. to Give As and Bi Halides. 2.4.6.2. by Hydrogen Halides 2.4.6.2.1. to Give Bismuth Chlorides. 2.4.6.3. by Other Halides 2.4.6.3.1. to Give Nitrogen Halides. 2.4.6.3.2. to Give Phosphorus Halides. 2.4.6.3.3. to Give As Halides. 2.4.7. from Cleavage of the Group VB - Oxygen Bond 2.4.7.1. by Halogens. 2.4.7.2. by Hydrogen Halides 2.4.7.2.1. to Give the Nitrogen - Halogen Bond. 2.4.7.2.2. to Give Phosphorus - Halogen Bond. 2.4.7.2.3. to Give the Arsenic - Halogen Bond. 2.4.7.2.4. to Give the Sb - and Bi - Halogen Bond. 2.4.7.3. by Other Halides. 2.4.8. from Cleavage of the Group VB - Other Group VIB Element Bond 2.4.8.1. by Halogens. 2.4.8.2. by Hydrogen Halides. 2.4.8.3. by Other Halides 2.4.8.3.1. to Give Phosphorus Fluorides from P - S and P - Se Bonds. 2.4.8.3.2. to Give Group VB - Chlorine Bonds. 2.4.8.3.3. to Give Group VB - Br and - I Bond. 2.4.9. from Cleavage of the Group VB - Nitrogen Bond 2.4.9.1. by Halogens. 2.4.9.2. by Hydrogen Halides. 2.4.9.3. by Other Halides. 2.4.10. from Cleavage of the Group VB - Other Group VB Element Bond 2.4.10.1. by Halogens 2.4.10.1.1. to Give Phosphorus Halides. 2.4.10.1.2. to Give As, Sb and Bi Halides. 2.4.10.2. by Hydrogen Halides 2.4.10.2.1. to Give Phosphorus Halides. 2.4.10.2.2. to Give As and Sb Halides. 2.4.10.3 by Other Halides 2.4.10.3.1. to Give Phosphorus Halides. 2.4.10.3.2. to Give As and Sb Haldies. 2.4.11. by Halide - Halide Exchange (Metathesis) (with or without Concomitant Redox) 2.4.11.1. by Metal Halides 2.4.11.1.1. of Group IA. 2.4.11.1.2. of Other than Group IA. 2.4.11.2. by Nonmetal Halides. 2.4.11.3. by Fluorine Derivatives 2.4.11.3.1. of Hydrogen, Ammonium and Potassium. 2.4.11.3.2. of Alkali Metals. 2.4.11.3.3. of Antimony. 2.4.11.3.4. of Arsenic(III). 2.4.11.3.5. of Other Metals. 2.4.11.3.6. of Potassium Sulfinate. 2.4.11.3.7. of Other Nonmetals. 2.4.12. from Cleavage of Other Element - Group VB Bonds (Including Scrambling) 2.4.12.1. by Halogens. 2.4.12.2. by Other Halides from Scrambling. 2.4.13. by Oxidative Halogenation of Low Valent Group VB Compounds 2.4.13.1. by Halogens 2.4.13.1.1. to Give the Nitrogen - Halogen Bond. 2.4.13.1.2. to Give the Group VB - Fluorine Bond. 2.4.13.1.3. to Give the Phosphorus - Chlorine Bond. 2.4.13.1.4. to Give the As - Cl Bond. 2.4.13.1.5. to Give the Sb - and Bi - Chlorine Bond. 2.4.13.1.6. to Give the Phosphorus - Bromine Bond. 2.4.13.1.7. to Give the As - Br Bond. 2.4.13.1.8. to Give the Sb - or Bi - Br Bond. 2.4.13.1.9. to Give the Group VB - Iodine Bond. 2.4.13.2. by Hydrogen Halides. 2.4.13.3. by Other Halides 2.4.13.3.1. to Give the Fluorine - Group VB Bond. 2.4.13.3.2. to Give the Chlorine - Group VB Bond. 2.4. Formation of Bonds between Halogens and Group VB (N, P, As, Sb, Bi) Elements 2.4.13.3.3. to Give Br and I Group VB Bonds. 2.4.14. Preparation of Astatine - Group VB Element Bonds 2.5. The Formation of the Halogen - Group IVB (C, Si, Ge, Sn, Pb) Element Bond 2.5.1. Introduction 2.5.2. from the Elements. 2.5.3. from Halogenation of the Group IVB Elements 2.5.3.1. by Hydrogen Halides. 2.5.3.2. by Various Halides. 2.5.3.3. by Organic Halides 2.5.3.3.1. with Elemental Si. 2.5.3.3.2. with Elemental Ge. 2.5.3.3.3. with Elemental Tin. 2.5.3.3.4. with Lead Metal. 2.5.4. by Other Halogenating Agents. 2.5.5. from Cleavage of the Group IVB - Hydrogen Bond 2.5.5.1. by Halogens. 2.5.5.2. by Hydrogen Halides. 2.5.5.3. by Other Halides. 2.5.6. from Cleavage of the Group IVB - Carbon Bond 2.5.6.1. the Si - Carbon Bond 2.5.6.1.1. by Halogens. 2.5.6.1.2. by Hydrogen and Alkyl Halides. 2.5.6.1.3. by Other Halides. 2.5.6.2. the Ge - Carbon Bond 2.5.6.2.1. by Halogens. 2.5.6.2.2. by Hydrogen and Alkyl Halides. 2.5.6.2.3. by Other Halides. 2.5.6.3. Cleavage of the Tin - Carbon Bond 2.5.6.3.1. by Halogens. 2.5.6.3.2. by Hydrogen Halides. 2.5.6.3.3. by Organic Halides. 2.5.6.3.4. by Other Halides. 2.5.6.4. of the Lead - Carbon Bond 2.5.6.4.1. by Halogens. 2.5.6.4.2. by Hydrogen and Alkyl Halides. 2.5.6.4.3. by Other Halides. 2.5.7. from Cleavage of the Group IVB - Other Group IVB Element Bond 2.5.7.1. the Si - Si Bond. 2.5.7.2. the Si - Sn Bond. 2.5.7.3. the Ge - Ge Bond. 2.5.7.4. the Ge - Sn Bond. 2.5.7.5. the Ge - Pb Bond. 2.5.7.6. the Sn - Sn Bond 2.5.7.6.1. by Halogens. 2.5.7.6.2. by Hydrogen, Alkyl and Other Halides. 2.5.7.7. the Pb - Pb Bond. 2.5.7.7.1. by Halogens. 2.5.7.7.2. by Hydrogen Halides. 2.5.7.7.3. by Other Halides. 2.5.8. from Cleavage of the Oxygen - 2.5.8.1. Si Bond 2.5.8.1.1. by Halogens. 2.5.8.1.2. by Halogens in the Presence of a Reducing Agent. 2.5.8.1.3. by Hydrogen Halides. 2.5.8.1.4. by Organic Halides. 2.5.8.1.5. by Other Halides. 2.5.8.2. Ge Bond 2.5.8.2.1. by Hydrogen Halides. 2.5.8.2.2. by Organic Halides. 2.5.6.2.3. by Other Halides. 2.5.8.3. Sn Bond 2.5.8.3.1. by Hydrogen Halides. 2.5.8.3.2. by Other Halides. 2.5.8.4. Pb Bond. 2.5.9. from Cleavage of the Group IVB - Group VIB Element Bond 2.5.9.1. by Halogens. 2.5.9.2. by Hydrogen Halides. 2.5.9.3. by Other Halides. 2.5.10. from Cleavage of Group IVB - Nitrogen Bond 2.5.10.1. by Halogens. 2.5.10.2. by Hydrogen Halides. 2.5. The Formation of the Halogen - Group IVB (C, Si, Ge, Sn, Pb) Element Bond 2.5.10.3. by Other Halides. 2.5.11. from Cleavage of the Group IVB Group VB Element Bond 2.5.11.1. by Halogens. 2.5.11.2. by Hydrogen Halides. 2.5.11.3. by Other Halides. 2.5.12. Group IVB Halides by Halide - Halide Exchange Reactions (Metathesis) 2.5.12.1. by Metal Halides 2.5.12.1.1. of the Alkali or Alkaline Earths. 2.5.12.1.2. by Silver and Other Transition Metal Halides. 2.5.12.1.3. by Halides. 2.5.12.2. by Metathesis Using Nonmetal Halides 2.5.12.2.1. Exchange with Halogens or Interhalogen Compounds. 2.5.12.2.2. by Hydrogen Halides. 2.5.12.2.3. by Other Nonmetal Halides Including Exchange Redistribution. 2.5.12.3. by Fluorinating Agents 2.5.12.3.1. That Utilize SbF3 or Antimony(V) Halides. 2.5.12.3.2. by HF. 2.5.12.3.3. by Other Metal - Fluorine Derivatives and NH4F. 2.5.12.3.4. by Fluorine Extraction from Fluorine containing Anions. 2.5.12.3.5. with Covalent Fluorides. 2.5.13. Cleavage of Other Group IVB Element Bonds (Cleavage of Group IVB Element - Metal Bonds) 2.5.13.1. by Halogens. 2.5.13.1.1. Cleavage of Carbon - Metal Bonds. 2.5.13.1.2. with Compounds that Contain Lower Group IVB Element - Transition Metal Bonds 2.5.13.1.3. Hydrogen Halides with Lower Group IVB Element - Metal Bonds 2.5.13.1.4. Hg(II) Halides with Lower Group lVB - Metal Bonds. 2.5.13.1.5. of Covalent Halides with Group IVB - Metal Bonds. 2.5.14. from Oxidative Halogenation of Compounds of Low Valent Group IVB Elements (Including Addition Reactions toC - C Multiple Bonds) 2.5.14.1. by Halogens. 2.5.14.2. by Hydrogen Halides. 2.5.14.3. by Other Covalent Halides. 2.5.15. Halides of Low Valent Group IVB Elements 2.5.15.1. Divalent Carbon Halides 2.5.15.1.1. Mono and Di halocarbenes 2.5.15.1.2. Alkyl and Aryl Halocarbenes. 2.5.15.2. Divalent Silicon Halides (Dihalosilylenes, Silicon Dihalides) 2.5.15.2.1. by Reduction. 2.5.15.2.2. by Thermal and Other Methods. 2.5.15.3. Divalent Germanium Halides (Dihalogermylenes, Germanium Dihalides, Organohalogermylenes. 2.5.15.4. Divalent Sn Halides. 2.5.16. Lead(II) Halides, PbX2 (X = F, Cl, Br, I) and Organolead(II) Halides. 2.5.17. Preparation of Astatine - Group IVB Element Bonds 2.5.17.1. Preparation of Astatine - Carbon Bonds 2.5.17.1.1. by Homogeneous and Heterogeneous Halogen Exchange 2.5.17.1.2. by Decomposition of Diazonium Salts. 2.5.17.1.3. from Organometallic Compounds 2.5.17.1.4. by Electrophilic Substitution After Chemical or Electrochemical Oxidation. 2.5.17.1.5. Hot Atom Reactions. 2.5.17.2. Preparation of Astatine Lead Bonds. List of Abbreviations Author index Compound Index Subject Index