| Preface |
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xiii | |
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Introduction to Inorganic Chemistry |
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1 | (14) |
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What is Inorganic Chemistry? |
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1 | (1) |
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Contrasts with Organic Chemistry |
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1 | (4) |
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Genesis of the Elements (The Big Bang) and Formation of the Earth |
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5 | (3) |
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Nuclear Reactions and Radioactivity |
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8 | (1) |
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Distribution of Elements on Earth |
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9 | (2) |
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The History of Inorganic Chemistry |
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11 | (4) |
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15 | (36) |
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Historical Development of Atomic Theory |
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15 | (6) |
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16 | (1) |
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Discovery of Subatomic Particles and the Bohr Atom |
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17 | (4) |
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21 | (22) |
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23 | (2) |
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Quantum Numbers and Atomic Wave Functions |
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25 | (9) |
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34 | (4) |
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38 | (5) |
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Periodic Properties of Atoms |
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43 | (8) |
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43 | (1) |
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44 | (1) |
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44 | (7) |
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51 | (25) |
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Lewis Electron-Dot Diagrams |
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51 | (6) |
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52 | (1) |
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53 | (1) |
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53 | (3) |
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Multiple Bonds in Be and B Compounds |
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56 | (1) |
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Valence Shell Electron Pair Repulsion Theory |
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57 | (10) |
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59 | (3) |
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62 | (1) |
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Electronegativity and Atomic Size Effects |
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63 | (3) |
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66 | (1) |
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67 | (2) |
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69 | (7) |
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Symmetry and Group Theory |
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76 | (40) |
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Symmetry Elements and Operations |
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76 | (6) |
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82 | (10) |
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Groups of Low and High Symmetry |
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84 | (2) |
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86 | (6) |
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Properties and Representations of Groups |
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92 | (10) |
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92 | (2) |
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Representations of Point Groups |
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94 | (3) |
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97 | (5) |
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Examples and Applications of Symmetry |
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102 | (14) |
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102 | (1) |
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103 | (13) |
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116 | (49) |
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Formation of Molecular Orbitals from Atomic Orbitals |
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116 | (6) |
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Molecular Orbitals from s Orbitals |
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117 | (2) |
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Molecular Orbitals from p Orbitals |
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119 | (1) |
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Molecular Orbitals from d Orbitals |
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120 | (2) |
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Nonbonding Orbitals and Other Factors |
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122 | (1) |
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Homonuclear Diatomic Molecules |
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122 | (12) |
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122 | (2) |
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124 | (1) |
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First and Second Row Molecules |
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125 | (5) |
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Photoelectron Spectroscopy |
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130 | (2) |
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132 | (2) |
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Heteronuclear Diatomic Molecules |
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134 | (5) |
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134 | (4) |
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Ionic Compounds and Molecular Orbitals |
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138 | (1) |
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Molecular Orbitals for Larger Molecules |
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139 | (22) |
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140 | (3) |
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143 | (5) |
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148 | (3) |
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151 | (3) |
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154 | (3) |
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157 | (1) |
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157 | (4) |
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Expanded Shells and Molecular Orbitals |
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161 | (4) |
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Acid-Base and Donor-Acceptor Chemistry |
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165 | (42) |
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Acid-Base Concepts as Organizing Concepts |
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165 | (1) |
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165 | (1) |
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166 | (13) |
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166 | (1) |
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167 | (1) |
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168 | (2) |
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170 | (1) |
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Frontier Orbitals and Acid-Base Reactions |
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171 | (3) |
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174 | (4) |
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Electronic Spectra (Including Charge Transfer) |
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178 | (1) |
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Hard and Soft Acids and Bases |
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179 | (13) |
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Theory of Hard and Soft Acids and Bases |
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183 | (4) |
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187 | (5) |
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192 | (15) |
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Measurement of Acid-Base Interactions |
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192 | (1) |
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Thermodynamic Measurements |
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193 | (1) |
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194 | (1) |
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Acidity and Basicity of Binary Hydrogen Compounds |
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194 | (2) |
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196 | (1) |
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196 | (1) |
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Acidity of Cations in Aqueous Solution |
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197 | (2) |
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199 | (1) |
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Solvation and Acid-Base Strength |
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200 | (1) |
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Nonaqueous Solvents and Acid-Base Strength |
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201 | (2) |
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203 | (4) |
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The Crystalline Solid State |
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207 | (33) |
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207 | (13) |
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207 | (7) |
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Structures of Binary Compounds |
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214 | (4) |
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218 | (1) |
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218 | (2) |
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Thermodynamics of Ionic Crystal Formation |
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220 | (3) |
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Lattice Energy and Madelung Constant |
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220 | (2) |
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Solubility, Ion Size (Large-Large and Small-Small), and HSAB |
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222 | (1) |
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Molecular Orbitals and Band Structure |
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223 | (5) |
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Diodes, The Photovoltaic Effect, and Light-Emitting Diodes |
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226 | (2) |
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228 | (3) |
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Low-Temperature Superconducting Alloys |
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228 | (1) |
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The Theory of Superconductivity (Cooper Pairs) |
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229 | (1) |
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High-Temperature Superconductors (YBa2Cu3O7 and Related Compounds) |
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230 | (1) |
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Bonding in Ionic Crystals |
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231 | (1) |
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231 | (1) |
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232 | (8) |
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Chemistry of the Main Group Elements |
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240 | (59) |
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General Trends in Main Group Chemistry |
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241 | (6) |
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241 | (2) |
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243 | (1) |
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244 | (1) |
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244 | (3) |
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247 | (2) |
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248 | (1) |
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Group 1 (IA): The Alkali Metals |
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249 | (4) |
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249 | (1) |
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250 | (3) |
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Group 2 (IIA): The Alkaline Earths |
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253 | (3) |
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253 | (1) |
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254 | (2) |
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256 | (5) |
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256 | (4) |
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Other Chemistry of the Group 13 (IIIA) Elements |
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260 | (1) |
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261 | (11) |
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261 | (6) |
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267 | (5) |
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272 | (7) |
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272 | (2) |
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274 | (5) |
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279 | (6) |
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279 | (6) |
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Group 17 (VIIA): The Halogens |
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285 | (6) |
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285 | (6) |
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Group 18 (VIIIA): The Noble Gases |
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291 | (8) |
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291 | (1) |
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292 | (7) |
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Coordination Chemistry I: Structures and Isomers |
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299 | (38) |
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299 | (5) |
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304 | (5) |
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309 | (14) |
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310 | (1) |
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Four-Coordinate Complexes |
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310 | (1) |
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311 | (1) |
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311 | (4) |
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Combinations of Chelate Rings |
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315 | (3) |
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318 | (1) |
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319 | (3) |
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Experimental Separation and Identification of Isomers |
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322 | (1) |
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Coordination Numbers and Structures |
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323 | (14) |
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Low Coordination Numbers (CN = 1, 2, and 3) |
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325 | (2) |
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327 | (1) |
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328 | (1) |
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329 | (2) |
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331 | (1) |
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332 | (1) |
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Larger Coordination Numbers |
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333 | (4) |
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Coordination Chemistry II: Bonding |
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337 | (42) |
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Experimental Evidence for Electronic Structures |
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337 | (5) |
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337 | (2) |
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339 | (3) |
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342 | (1) |
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Coordination Numbers and Molecular Shapes |
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342 | (1) |
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Theories of Electronic Structure |
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342 | (3) |
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342 | (1) |
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343 | (2) |
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345 | (17) |
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Molecular Orbitals for Octahedral Complexes |
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345 | (1) |
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Orbital Splitting and Electron Spin |
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346 | (4) |
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Ligand Field Stabilization Energy |
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350 | (2) |
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352 | (4) |
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356 | (4) |
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360 | (2) |
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362 | (8) |
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362 | (2) |
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364 | (2) |
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366 | (1) |
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Types of Ligands and the Spectrochemical Series |
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367 | (1) |
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Magnitudes of eσ, eπ, and Δ |
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368 | (2) |
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370 | (3) |
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Four- and Six- Coordinate Preferences |
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373 | (2) |
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375 | (4) |
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Coordination Chemistry III: Electronic Spectra |
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379 | (33) |
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380 | (2) |
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Beer-Lambert Absorption Law |
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380 | (2) |
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Quantum Numbers of Multielectron Atoms |
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382 | (6) |
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387 | (1) |
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Electronic Spectra of Coordination Compounds |
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388 | (24) |
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390 | (1) |
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391 | (2) |
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393 | (5) |
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Jahn-Teller Distortions and Spectra |
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398 | (3) |
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Examples of Applications of Tanabe-Sugano Diagrams: Determining Δ0 from Spectra |
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401 | (5) |
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406 | (1) |
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407 | (5) |
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Coordination Chemistry IV: Reactions and Mechanisms |
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412 | (42) |
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412 | (2) |
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414 | (3) |
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Inert and Labile Compounds |
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414 | (1) |
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Mechanisms of Substitution |
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415 | (2) |
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Kinetic Consequences of Reaction Pathways |
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417 | (3) |
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417 | (1) |
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418 | (1) |
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419 | (1) |
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Experimental Evidence in Octahedral Substitution |
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420 | (9) |
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420 | (3) |
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Linear Free Energy Relationships |
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423 | (2) |
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425 | (1) |
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The Conjugate Base Mechanism |
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426 | (2) |
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The Kinetic Chelate Effect |
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428 | (1) |
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Stereochemistry of Reactions |
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429 | (5) |
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Substitution in trans Complexes |
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430 | (2) |
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Substitution in cis Complexes |
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432 | (1) |
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Isomerization of Chelate Rings |
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433 | (1) |
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Substitution Reactions of Square-Planar Complexes |
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434 | (3) |
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Kinetics and Stereochemistry of Square-Planar Substitutions |
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434 | (1) |
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Evidence for Associative Reactions |
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435 | (2) |
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437 | (3) |
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Explanations of the trans Effect |
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439 | (1) |
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Oxidation-Reduction Reactions |
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440 | (6) |
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Inner-and Outer-Sphere Reactions |
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441 | (4) |
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Conditions for High and Low Oxidation Numbers |
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445 | (1) |
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Reactions of Coordinated Ligands |
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446 | (8) |
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Hydrolysis of Esters, Amides, and Peptides |
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446 | (2) |
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448 | (1) |
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Electrophilic Substitution |
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449 | (5) |
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454 | (66) |
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457 | (1) |
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Organic Ligands and Nomenclature |
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458 | (2) |
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460 | (7) |
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460 | (3) |
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463 | (2) |
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465 | (2) |
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Ligands in Organometallic Chemistry |
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467 | (15) |
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467 | (8) |
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475 | (2) |
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Hydride and Dihydrogen Complexes |
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477 | (2) |
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Ligands Having Extended π Systems |
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479 | (3) |
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Bonding Between Metal Atoms and Organic Π Systems |
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482 | (14) |
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482 | (3) |
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485 | (7) |
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492 | (4) |
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Complexes Containing M---C, M = C, and M ≡ C Bonds |
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496 | (7) |
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Alkyl and Related Complexes |
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496 | (2) |
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498 | (3) |
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Carbyne (Alkylidyne) Complexes |
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501 | (2) |
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Spectral Analysis and Characterization of Organometallic Complexes |
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503 | (17) |
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503 | (4) |
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507 | (2) |
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Examples of Characterization |
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509 | (11) |
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Organometallic Reactions and Catalysis |
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520 | (36) |
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Reactions Involving Gain or Loss of Ligands |
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520 | (8) |
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Ligand Dissociation and Substitution |
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521 | (3) |
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524 | (1) |
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525 | (1) |
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Nucleophilic Displacement |
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526 | (2) |
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Reactions Involving Modification of Ligands |
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528 | (6) |
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528 | (1) |
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Carbonyl Insertion (Alkyl Migration) |
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528 | (5) |
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533 | (1) |
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533 | (1) |
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534 | (1) |
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534 | (14) |
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Example of Catalysis: Catalytic Deuteration |
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535 | (1) |
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535 | (3) |
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Monsanto Acetic Acid Process |
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538 | (3) |
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541 | (1) |
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Hydrogenation by Wilkinson's Catalyst |
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542 | (2) |
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544 | (4) |
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548 | (8) |
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Ziegler-Natta Polymerizations |
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548 | (1) |
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549 | (7) |
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Parallels Between Main Group and Organometallic Chemistry |
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556 | (38) |
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Main Group Parallels with Binary Carbonyl Complexes |
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556 | (2) |
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558 | (8) |
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Extensions of the Analogy |
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561 | (4) |
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Examples of Applications of the Analogy |
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565 | (1) |
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566 | (6) |
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Multiple Metal-Metal Bonds |
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568 | (4) |
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572 | (22) |
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572 | (5) |
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577 | (2) |
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Metallaboranes and Metallacarboranes |
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579 | (3) |
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582 | (5) |
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587 | (1) |
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Additional Comments on Clusters |
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588 | (6) |
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Bioinorganic and Environmental Chemistry |
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594 | (43) |
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Porphyrins and Related Complexes |
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596 | (8) |
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597 | (3) |
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600 | (4) |
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604 | (2) |
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606 | (5) |
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611 | (5) |
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616 | (2) |
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Inorganic Medicinal Compounds |
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618 | (4) |
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Cisplatin and Related Complexes |
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618 | (4) |
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Auranofin and Arthritis Treatment |
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622 | (1) |
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Vanadium Complexes in Medicine |
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622 | (1) |
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Study of DNA Using Inorganic Agents |
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622 | (2) |
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624 | (13) |
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624 | (5) |
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629 | (8) |
| Appendix A Answers to Exercises |
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637 | (31) |
| Appendix B-1 Ionic Radii |
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668 | (3) |
| Appendix B-2 Ionization Energy |
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671 | (1) |
| Appendix B-3 Electron Affinity |
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672 | (1) |
| Appendix B-4 Electronegativity |
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673 | (1) |
| Appendix B-5 Absolute Hardness Parameters |
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674 | (1) |
| Appendix B-6 CA, EA, CB, and EB Values |
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675 | (1) |
| Appendix B-7 Latimer Diagrams for Selected Elements |
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676 | (5) |
| Appendix C Character Tables |
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681 | (10) |
| Appendix D Electron-Dot Diagrams and Formal Charge |
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691 | (6) |
| Index |
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697 | |
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