Inorganic Chemistry of Main Group Elements R. Bruce King Bibliothek Fachbereicti Chemie Technische Universitat Darmstadt VCH Jnventar Nr. Contents Introduction and General Organization xiii 1. Hydrogen 1 1.1 General Aspects of Hydrogen Chemistry 1 1.2 Hydrogen Isotopes and Elemental Hydrogen 1.3 Hydrogen Bonding 5 1.4 Pro tic Acids and Solvents 8 1.5 Binary and Ternary Metallic Hydrides 15 References 18 2. Carbon 21 2.1 General Aspects of Carbon Chemistry 21 2.2 Carbon Isotopes and Elemental Carbon 22 2.3 Carbides 26 2.4 Carbon Halides 28 2.5 Carbon Oxides, Carbonic Acid, and Oxocarbon Anions 30 2.6 Cyanides and Related Compounds 34 2.7 Carbon-Sulfur Derivatives 38 References 40 viii INORGANIC CHEMISTRY OF MAIN GROUP ELEMENTS 3. Silicon, Germanium, Tin, and Lead 43 3.1 General Aspects of the Chemistry of Silicon, Germanium, Tin, and Lead 43 3.2 Elemental Silicon, Germanium, Tin, and Lead 44 3.3 Anions and Related Binary Compounds of Silicon, Germanium, Tin, and Lead 45 3.4 Hydrides and Halides of Silicon, Germanium, Tin, and Lead 47 3.5 Silicates and Related Oxygen Compounds of Silicon 50 3.6 Other Oxygen Compounds of Silicon, Germanium, Tin, and Lead 56 3.7 Organometallic Derivatives of Silicon, Germanium, Tin, and Lead 57 3.8 Divalent Compounds of Silicon, Germanium, Tin, and Lead 61 References 63 4. Nitrogen 67 4.1 General Aspects of the Chemistry of Nitrogen 67 4.2 Nitrogen Isotopes and Elemental Nitrogen 69 4.3 Nitrides 71 4.4 Compounds of Nitrogen with Hydrogen 72 4.5 Oxides of Nitrogen 78 4.6 Oxoacids and Oxoanions of Nitrogen 83 4.7 Nitrogen-Halogen Compounds 86 References 89 5. Phosphorus, Arsenic, Antimony, and Bismuth 91 5.1 General Aspects of the Chemistry of Phosphorus, Arsenic, Antimony, and Bismuth 91 5.2 Elemental Phosphorus, Arsenic, Antimony, and Bismuth 94 5.3 Phosphides, Arsenides, Antimonides, and Bismuthides 96 5.4 Hydrides of Phosphorus, Arsenic, Antimony, and Bismuth 97 5.5 Halides of Phosphorus, Arsenic, Antimony, and Bismuth 99 5.6 Oxides of Phosphorus, Arsenic, Antimony, and Bismuth 105 5.7 Sulfides and Other Chalcogenides of Phosphorus, Arsenic, Antimony, and Bismuth 108 5.8 Oxoacids of Phosphorus and Their Derivatives 109 5.9 Oxoacids and Oxoanions of Arsenic, Antimony, and Bismuth 115 5.10 Phosphorus-Nitrogen Compounds 116 5.11 Organic Derivatives of Phosphorus, Arsenic, Antimony, and Bismuth 119 CONTENTS 5.12 Cationic Chemistry of Phosphorus, Arsenic, Antimony, and Bismuth in Aqueous Solution 124 References 126 6. The Chalcogens 129 6.1 General Aspects of Chalcogen Chemstry 129 6.2 The Elemental Chalcogens 133 6.3 Compounds with Oxygen-Oxygen Bonds and Related Compounds 141 6.4 Binary Compounds of Sulfur and Its Heavier Congeners with Hydrogen and Metals 146 6.5 Sulfur-Nitrogen Compounds 148 6.6 Halides of Sulfur and Its Congeners 151 6.7 Oxides of Sulfur and Its Congeners 158 6.8 Oxoacids and Oxoanions of Sulfur, Selenium, and Tellurium 161 6.9 Miscellaneous Selenium and Tellurium Compounds 167 References 169 7. Halogens and the Noble Gases 173 7.1 General Aspects of Halogen and Noble Gas Chemistry 173 7.2 The Elemental Halogens and Noble Gases 174 7.3 Halides 177 7.4 Halogen Oxides 180 7.5 Halogen Oxoacids and Anions 182 7.6 Interhalogen and Polyhalogen Compounds, Cations, and Anions 187 7.7 Other Halogen Compounds 191 7.8 Noble Gas Compounds 193 References 197 8. Boron 199 8.1 General Aspects of Boron Chemistry 199 8.2 Elemental Boron and Metal Borides 201 8.3 Boranes and Related Compounds 203 8.4 Boron Halides and Their Derivatives 217 8.5 Boron-Oxygen Compounds 220 8.6 Organoboron Compounds 223 8.7 Boron-Nitrogen Derivatives 226 References 230 t INORGANIC CHEMISTRY OF MAIN GROUP ELEMENTS 9. Aluminum, Gallium, Indium, and Thallium 233 9.1 General Aspects of the Chemistry of Aluminum, Gallium, Indium, and Thallium 233 9.2 The Elements and Their Alloys 234 9.3 Aqueous Solution Chemistry of Trivalent Aluminum, Gallium, Indium, and Thallium 236 9.4 Oxygen Derivatives of Trivalent Aluminum, Gallium, Indium, and Thallium 238 9.5 Halogen Derivatives of Trivalent Aluminum, Gallium, Indium, and Thallium 241 9.6 Hydride Derivatives of Trivalent Aluminum, Gallium, Indium, and Thallium 243 9.7 Other Binary Compounds of Aluminum, Gallium, Indium, and Thallium 245 9.8 Organometallic Compounds of Aluminum, Gallium, Indium, and Thallium 246 9.9 Aluminum, Gallium, Indium, and Thallium with Oxidation States Below 3 249 References 251 10. The Alkali and Alkaline Earth Metals 255 10.1 General Aspects of the Chemistry of the Alkali and Alkaline Earth Metals 255 10.2 The Free Alkali and Alkaline Earth Metals 257 10.3 Compounds of the Alkali Metals 261 10.4 Beryllium Chemistry 266 10.5 Chemistry of Magnesium, Calcium, Strontium, and Barium 268 References 272 11. Zinc, Cadmium, and Mercury 273 11.1 General Aspects of the Chemistry of Zinc, Cadmium, and Mercury 273 11.2 Elemental Zinc, Cadmium, and Mercury 274 11.3 Divalent Zinc and Cadmium Compounds 275 11.4 Divalent Mercury Compounds 278 11.5 Organometallic Compounds of Zinc, Cadmium, and Mercury 281 11.6 Zinc, Cadmium, and Mercury with Oxidation States Below 2 285 References 287 CONTENTS 12. Lanthanides and Actinides 289 12.1 General Aspects of the Chemistry of Lanthanides and Actinides 289 12.2 The Lanthanide and Actinide Metals 296 12.3 Trivalent Lanthanides 297 12.4 Tetravalent and Divalent Lanthanides 298 12.5 Actinide Chemistry 299 12.6 Organometallic Chemistry of Lanthanides and Actinides 302 References 305 Index 309.