Inorganic Reactions and Methods Volume 2

Inorganic Reactions and Methods Volume 2 The Formation of the Bond to Hydrogen (Part 2) Editor J.J. Zuckerman Subject Index Editor A.P. Hagen

Contents of Volume 2 How to Use this Book Preface to the Series Editorial Consultants to the Series Contributors to Volume 2 xin xix xxiii xxv 1. The Formation of the Bond to Hydrogen (Part 2) 1 1-5. Formation of Bonds between Hydrogen and Elements of Group VB (N, P, As, Sb, Bi) 3 1.5.1. 1.5.2. 1.5.2.1. 1.5.2.1.1. 1.5.2.1.2. 1.5.2.2. 1.5.2.3. 1.5.2.4. 1.5.2.5. 1.5.3. 1.5.3.1. 1.5.3.1.1. 1.5.3.1.2. 1.5.3.1.3. 1.5.3.2. 1.5.3.2.1. 1.5.3.2.2. 1.5.3.2.3. 1.5.3.3. 1.5.3.3.1. 1.5.3.3.2. 1.5.3.3.3. by Reaction of Hydrogen with Nitrogen from the Elements. from Compounds. with Phosphorus. with Arsenic. with Antimony. with Bismuth. by Protonation of Nitrogen in Aqueous Systems. in Other Protonic Solvents. with Protonic Acids in Nonprotonic Solvents. of Phosphorus and Phosphorous Compounds in Aqueous Systems. in Other Protonic Solvents. with Protonic Acids in Nonprotonic Solvents. of Arsenic and Arsenic Compounds in Aqueous Systems. in Other Protonic Solvents. with Protonic Acids in Nonprotonic Solvents. 3 3 3 3 4 5 6 6 6 7 7 7 10 12 18 18 21 22 30 30 31 32 V

vi Contents of Volume 2 Formation of Bonds between Hydrogen and Elements of Group VB (N, P, As, Sb, Bi) 1.5.3.4. 1.5.3.5. 1.5.4. 1.5.4.1. 1.5.4.1.1. 1.5.4.1.2. 1.5.4.1.3. 1.5.4.1.4. 1.5.4.2. 1.5.4.2.1. 1.5.4.2.2. 1.5.4.2.3. 1.5.4.2.4. 1.5.4.3. 1.5.4.4. 1.5.4.5. 1.5.5. 1.5.5.1. 1.5.5.2. 1.5.5.2.1. 1.5.5.2.2. 1.5.5.2.3. 1.5.5.3. 1.5.5.3.1. 1.5.5.3.2. 1.5.5.4. 1.5.5.5. 1.5.6. 1.5.6.1. 1.5.6.2. 1.5.6.3. 1.5.6.4. 1.5.7. 1.5.7.1. 1.5.7.1.1. 1.5.7.1.2. 1.5.7.1.3. 1.5.7.1.4. 1.5.7.1.5. 1.5.7.2. 1.5.7.2.1. of Antimony. of Bismuth. by Reactions of Hydrides with Compounds of Nitrogen Invoiving Binary lonic Hydrides. Involving Binary Covalent Hydrides. Invoiving Exchange-Cleavage. Involving Redistribution- Disproportionation. with Compounds of Phosphorus Involving lonic Hydrides. Involving Covalent Hydrides. Involving Exchange. Involving Redistribution- Disproportionation. with Compounds of Arsenic. with Compounds of Antimony. with Compounds of Bismuth. by Reaction of Complex Hydrides with Compounds of Nitrogen. with Compounds of Phosphorus Involving Halides. Involving Oxygen Compounds. Involving Other Derivatives. with Compounds of Arsenic Involving Halides. Involving Oxygen Compounds. with Compounds of Antimony. with Compounds of Bismuth. by Industrial Processes with Compounds of Nitrogen. with Compounds of Phosphorus. with Compounds of Arsenic. with Compounds of Antimony. The Synthesis of Deuterium Derivatives by Interconversion of Deuterated Compounds Involving Nitrogen. Involving Phosphorus. Involving Arsenic. Involving Antimony. Involving Bismuth. by Isotopic Enrichment Using Chemical Reactions of Nitrogen Compounds. 33 34 34 34 34 35 36 37 38 38 39 41 41 43 44 45 45 45 46 46 48 49 50 50 51 51 53 53 53 55 57 57 58 58 58 59 60 61 61 61 61

Contents of Volume 2 VII 1.5.7.2.2. of Phosphorous Compounds. 62 1.5.7.2.3. of Arsenic Compounds. 63 1.6. Formation of Bonds between Hydrogen and Elements of Group IVB (C, Si, Ge, Sn, Pb) 64 1.6.1. 1.6.2. 1.6.2.1. 1.6.2.1.1. 1.6.2.1.2. 1.6.2.2. 1.6.2.3. 1.6.2.4. 1.6.2.5. 1.6.3. 1.6.3.1. 1.6.3.1.1. 1.6.3.1.2. 1.6.3.1.3. 1.6.3.2. 1.6.3.2.1. 1.6.3.2.2. 1.6.3.2.3. 1.6.3.3. 1.6.3.3.1. 1.6.3.3.2. 1.6.3.3.3. 1.6.3.4. 1.6.3.4.1. 1.6.3.4.2. 1.6.3.4.3. 1.6.3.5. 1.6.4. 1.6.4.1. 1.6.4.1.1. 1.6.4.1.2. 1.6.4.1.3. 1.6.4.1.4. 1.6.4.1.5. 1.6.4.2. 1.6.4.2.1. 1.6.4.2.2. 1.6.4.2.3. from the Elements Giving Hydrides of Carbon from Elemental Carbon. from Elemental Hydrogen. Giving Hydrides of Silicon. Giving Hydrides of Germanium. Giving Hydrides of Tin. Giving Hydrides of Lead. by Reactions of Group IVB Anionic Derivatives Giving Carbides from Protonic Species in Water. from Protonic Species in Liquid Ammonia. from Protonic Species in Other Solvents. Giving Silicides from Protonic Species in Water. from Protonic Species in Liquid Ammonia. from Protonic Species in Other Solvents. Giving Germanides from Protonic Species in Water. from Protonic Species in Liquid Ammonia. from Protonic Acids in Other Solvents. Giving Stannides from Protonic Species in Water. from Protonic Species in Liquid Ammonia. from Protonic Species in Other Solvents. Giving Plumbides. by Reactions of Hydrides with Compounds of Carbon Giving Nitrogen Compounds. Giving Compounds with Carbon-Carbon Multiple Bonds. with Compounds of Silicon 64 64 64 64 66 68 69 72 72 75 75 76 76 77 77 78 79 80 80 81 81 82 82 82 82 83 85 86 88 90 90 91 92

1.6.4.3. 1.6.4.3.1. 1.6.4.3.2. 1.6.4.3.3. 1.6.4.4. 1.6.4.4.1. 1.6.4.4.2. 1.6.4.4.3. 1.6.4.5. 1.6.4.5.1. 1.6.4.5.2. 1.6.4.5.3. 1.6.5. 1.6.5.1. 1.6.5.1.1. 1.6.5.1.2. 1.6.5.1.3. 1.6.5.1.4. 1.6.5.2. 1.6.5.2.1. 1.6.5.2.2. 1.6.5.2.3. 1.6.5.3. 1.6.5.3.1. 1.6.5.3.2. 1.6.5.3.3. 1.6.5.4. 1.6.5.4.1. 1.6.5.4.2. 1.6.5.4.3. 1.6.5.5. 1.6.6. 1.6.6.1. 1.6.6.2. 1.6.6.3. 1.6.6.4. 1.6.7. 1.6.7.1. 1.6.7.1.1. 1.6.7.1.2. 1.6.7.1.3. 1.6.7.1.4. 1.6.7.1.5. Contents of Volume 2 Formation of Bonds between Hydrogen and Elements of Group IVB (C, Si, Ge, Sn, Pb) with Compounds of Germanium with Compounds of Tin Giving Oxygen Compounds with Compounds of Lead by Reactions of Complex Hydrides with Carbon Compounds Giving Nitrogen Compounds. Giving Compounds with Carbon-Carbon Multiple Bonds. with Silicon Compounds with Germanium Compounds with Tin Compounds with Lead Compounds. by Industrial Processes with Compounds of Carbon. with Compounds of Silicon. with Compounds of Germanium. with Compounds of Tin. The Synthesis of Deuterium Derivatives by Interconversion of Deuterated Compounds Involving Carbon. Involving Silanes. Involving Germanes. Involving Stannanes. Involving Plumbanes. 94 94 95 95 97 97 98 98 99 99 99 100 100 100 100 101 102 103 104 104 105 106 106 106 108 109 109 109 110 111 111 111 111 115 116 117 117 117 117 119 119 120 121

Contents of Volume 2 IX 1.6.7.2. by Isotopic Enrichment Using Chemical Reactions 121 1.6.7.2.1. of Carbon Compounds. 121 1.6.7.2.2. ofsilanes. 122 1.6.7.2.3. of Germanes. 123 1.7. Formation of Bonds between Hydrogen and Elements of Group HIB (B, AI, Ga, In, Tl) 124 1.7.1. 1.7.2. 1.7.3. 1.7.3.1. 1.7.3.2. 1.7.3.3. 1.7.4. 1.7.4.1. 1.7.4.1.1. 1.7.4.1.2. 1.7.4.1.3. 1.7.4.1.4. 1.7.4.2. 1.7.4.3. 1.7.4.4. 1.7.4.5. 1.7.5. 1.7.5.1. 1.7.5.2. 1.7.6. 1.7.7. 1.7.7.1. 1.7.7.2. from the Elements. from Group HIB Derivatives, Excluding Reactions of Hydrides and Complex Hydrides Involving the Borides. Involving the Reduction of Group HIB Derivatives with Covalent Hydrides. Involving Other Reactions. from the Hydride Ion with Compounds of Boron Involving Halides. Involving Oxygen Compounds. Involving Nitrogen Compounds. Involving Other Compounds. with Compounds of Aluminum. with Compounds of Gallium. with Compounds of Indium. with Compounds of Thallium. from Complex Hydrides with Compounds of Boron. with Compounds of Aluminum, Gallium, Indium and Thallium. by Industrial Processes. The Synthesis of Deuterium Derivatives by Isotopic Exchange. by Isotope Enrichment Using Chemical Reactions. 124 125 129 129 130 132 133 133 133 134 135 136 136 138 138 138 139 139 143 145 146 146 148 1.8. Formation of Bonds between Hydrogen and Metals of Group IA (Li, Na, K, Rb, Cs, Fr) or IIA (Be, Mg, Ca, Sn, Ba, Ra) 151 1.8.1. 1.8.2. 1.8.2.1. Alkali-Metal Hydrides Lithium Hydride 151 151 151

X Contents of Volume 2 Formation of Bonds between Hydrogen and Metals of Group IA (Li, Na, K, Rb, Cs, Fr) or IIA (Be, Mg, Ca, Sn, Ba, Ra) 1.8.2.2. Sodium, Potassium, Rubidium and Cesium Hydrides 153 1.8.3. Alkaline-Earth Metal Hydrides 156 1.8.3.1. Beryllium Hydride 156 1.8.3.2. Magnesium Hydride 157 1.8.3.3. Calcium, Strontium and Barium Hydrides 158 1.9. Formation of Bonds between Hydrogen and Metals of Group IB (Cu, Ag, Au) or IIB (Zn, Cd, Hg) 160 1.9.1. 1.9.2. 1.9.3. 1.9.4. 1.9.4.1. 1.9.4.2. 1.9.5. 1.9.5.1. 1.9.5.2. 1.9.6. from the Elements. by Reactions with Hydrogen Atoms and Ions with Compounds of Group IB. by Reactions of Hydride Ion with Compounds of Group IB. with Compounds of Group IIB. by Reactions with Neutral and Anionic Metal Hydrides with Compounds of Group IB. with Compounds of Group IIB. by Other Methods for Group IB and IIB Metal Hydrides. 160 160 161 161 161 161 162 162 168 172 1.10. Formation of Bonds between Hydrogen and Transition and Inner-Transition Metals 173 1.10.1. 1.10.2. 1.10.3. 1.10.3.1. 1.10.3.2. 1.10.3.3. 1.10.4. 1.10.4.1. 1.10.4.1.1. 1.10.4.1.2. from the Elements. by Hydrogenation of Metal Oxides. of Metal Salts. of Metal Carbonyls. by Oxidative Addition of Hydrogen to Neutral, Coordinatively Unsaturated Species Involving Iridium. Involving Platinum. 173 173 174 174 175 176 178 178 178 181

Contents of Volume 2 xi 1.10.4.1.3. Involving Rhodium. 183 1.10.4.1.4. Involving Fe Ir and Ta Ta Clusters. 184 1.10.4.2. to Cationic, Coordinatively and Unsaturated Species of Rhodium, Ruthenium and Iridium. 185 1.10.4.3. to Neutral Species with Replacement of Coordinated Ligands 186 1.10.4.3.1. Involving Niobium, Tantalum and Zirconium. 187 1.10.4.3.2. Involving Molybdenum and Rhenium. 187 1.10.4.3.3. Involving Ruthenium and Mixed Metal- Ruthenium Clusters. 188 1.10.4.3.4. Involving Iron, Osmium, Rhodium, Iridium and Platinum. 190 1.10.4.4. to Cationic Species of Iridium, Rhodium and Platinum with Replacement of Coordinated Ligands. 192 1.10.5. by Oxidative Addition to Metal Complexes 194 1.10.5.1. of Hydrogen Halides. 195 1.10.5.2. of Hydrogen-Boron Bonds. 196 1.10.5.3. of Hydrogen-Carbon Bonds. 197 1.10.5.4. of Hydrogen-Other Group IVB Element Bonds. 200 1.10.5.5. of Hydrogen-Group VB Element Bonds 201 1.10.5.5.1. Involving Hydrogen-Nitrogen Bonds. 201 1.10.5.5.2. Involving Hydrogen-Phosphorus Bonds. 201 1.10.5.6. of Hydrogen-Group VIB Element Bonds 202 1.10.5.6.1. Involving Hydrogen-Oxygen Bonds. 202 1.10.5.6.2. Involving Hydrogen-Sulfur Bonds. 203 1.10.6 by Protonation 204 1.10.6.1. of Neutral and Cationic Complexes in Acid 204 1.10.6.1.1. with Mononuclear Complexes: Scope. 204 1.10.6.1.2. with Mononuclear Complexes: Position of the Protonation Equilibria. 208 1.10.6.1.3. with Mononuclear Complexes: Rates. 209 1.10.6.1.4. with Polynuclear Complexes. 210 1.10.6.2. of Metal Anions 212 1.10.6.2.1. with Mononuclear Anions: Scope. 212 1.10.6.2.2. with Mononuclear Anions: Position of the Protonation Equilibira. 214 1.10.6.2.3. with Mononuclear Anions: Rates. 215 1.10.6.2.4. with Polynuclear Anions. 216 1.10.7. by Reduction of Metal Complexes 220 1.10.7.1. with Borohydride. 220 1.10.7.2. with Trialkylborohydride and Other Substituted Borohydrides. 223 1.10.7.3. with Tetrahydroaluminate. 224 1.10.7.4. with Alkoxyaluminum Hydrides. 225 1.10.8. by Hydrogen Transfer to the Metal 226 1.10.8.1. from Alcohols in Basic Media. 226

xii Contents of Volume 2 Formation of Bonds between Hydrogen and Transition and Inner-Transition Metals 1.10.8.2. 1.10.8.3. 1.10.8.4. 1.10.9. 1.11. 1.12. 1.12.1. 1.12.2. 1.12.3. 1.12.4. 1.12.4.1. 1.12.4.2. 1.12.5. 1.12.5.1. 1.12.5.2. 1.12.5.3. 1.12.6. 1.12.7. 1.12.7.1. 1.12.7.2. 1.12.7.3. 1.12.8. 1.12.8.1. 1.12.8.1.1. 1.12.8.1.2. 1.12.8.1.3. 1.12.8.2. 1.12.8.2.1. 1.12.8.2.2. 1.12.8.2.3. 1.12.8.2.4. from Hydrazine. from Aluminum Alkyls. from Alkyimagnesium Halides. by Decarboxylation of Hydroxycarbonyl or Formate Complexes Formation of Bonds between Hydrogen and Elements of Group 0 Formation of Reversible Metal Hydrides by Direct Reaction of Hydrogen with Alkali Metals. with Alkaline-Earth Metals. with Group IIIA Transition Metals Involving Lanthanides. Involving Actinides. with Group IVA Transition Metals Involving Titanium. Involving Zirconium. Involving Hafnium. with Group VA Transition Metals. with Groups VIA, VIIA and VIII Transition Metals Involving Chromium and Molybdenum. Involving Manganese and Technetium. Involving Nickel, Rhodium and Palladium. to Form Ternary Hydrides from Intermetallics Giving AM 5 Compounds. Giving AB 2 Compounds. Giving Hydrides of Other Intermetallics. from Metal-Nonmetal Systems Involving Carbides. Involving Oxides and Sulfides. Involving Nitrides and Phosphides. Involving Halides. 229 230 231 233 236 237 237 241 241 241 241 244 244 244 245 245 245 246 246 247 248 249 249 249 251 256 258 259 259 260 260 List of Abbreviations Author Index Compound Index Subject Index 263 269 309 467