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The Organometallic Chemistry of the Transition Metals


The Organometallic Chemistry of the Transition Metals


7. Aufl.

von: Robert H. Crabtree

88,99 €

Verlag: Wiley
Format: EPUB
Veröffentl.: 03.07.2019
ISBN/EAN: 9781119465867
Sprache: englisch
Anzahl Seiten: 464

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Beschreibungen

<p><b>Provides vital information on organometallic compounds, their preparation, and use in synthesis, and explores the fundamentals of the field and its modern applications</b></p> <p>Fully updated and expanded to reflect recent advances, the new, seventh edition of this bestselling text presents students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. Increased focus is given to organic synthesis applications, nanoparticle science, and green chemistry. This edition features up-to-date examples of fundamental reaction steps and greater emphasis on key topics like oxidation catalysis, CH functionalization, nanoclusters and nanoparticles, and green chemistry. New coverage is added for computational chemistry, energy production, and biochemical aspects of organometallic chemistry.</p> <p><i>The Organometallic Chemistry of the Transition Metals, Seventh Edition</i> provides new/enhanced chapter coverage of ligand-assisted additions and eliminations; proton-coupled electron transfer; surface, supported, and cooperative catalysis; green, energy, and materials applications; and photoredox catalysis. It covers coordination chemistry; alkyls and hydrides; Pi-complexes; and oxidative addition and reductive elimination. The book also features sections on insertion and elimination; spectroscopy; metathesis polymerization and bond activation; and more.</p> <ul> <li>Provides an excellent foundation of the fundamentals of organometallic chemistry</li> <li>Includes end-of-chapter problems and their solutions</li> <li>Expands and includes up-to-date examples of fundamental reaction steps and focuses on important topics such as oxidation catalysis, CH functionalization, nanoparticles, and green chemistry</li> <li>Features all new coverage for computational chemistry, energy production, and biochemical aspects of organometallic chemistry</li> </ul> <p><i>The Organometallic Chemistry of the Transition Metals, Seventh Edition</i> is an insightful book that will appeal to all advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry, as well as any practicing chemist in those fields.</p>
<p>Preface xi</p> <p>Acknowledgments xiii</p> <p>List of Abbreviations xv</p> <p><b>1 Introduction 1</b></p> <p>1.1 Why Study Organometallic Chemistry? 1</p> <p>1.2 Coordination Chemistry 3</p> <p>1.3 Werner Complexes 3</p> <p>1.4 The Trans Effect 7</p> <p>1.5 Soft Versus Hard Ligands 9</p> <p>1.6 The Crystal Field 10</p> <p>1.7 The Ligand Field 17</p> <p>1.8 Two-Electron Three-Center Bonding 19</p> <p>1.9 Four-Electron Three-Center Bonding 20</p> <p>1.10 Back Bonding 22</p> <p>1.11 Trends in d Orbital Energies 26</p> <p>1.12 Types of Ligand 27</p> <p>References 32</p> <p>Problems 33</p> <p><b>2 Making Sense of Organometallics 35</b></p> <p>2.1 The 18-Electron Rule 35</p> <p>2.2 Limitations of the 18-Electron Rule 43</p> <p>2.3 Electron Counting in Reactions 45</p> <p>2.4 The Oxidation State Concept and its Limitations 46</p> <p>2.5 Electroneutrality 52</p> <p>2.6 Coordination Number and Geometry 53</p> <p>2.7 Effects of Complexation 56</p> <p>2.8 Differences between Metals 58</p> <p>References 62</p> <p>Problems 63</p> <p><b>3 Alkyls and Hydrides 65</b></p> <p>3.1 Alkyls and Aryls 65</p> <p>3.2 Other σ-Bonded Ligands 79</p> <p>3.3 Metal Hydrides 80</p> <p>3.4 Sigma Complexes 83</p> <p>3.5 Bond Strengths 86</p> <p>References 88</p> <p>Problems 89</p> <p><b>4 Ligand Substitution 91</b></p> <p>4.1 Metal Carbonyls 91</p> <p>4.2 Phosphines 100</p> <p>4.3 <i>N</i>-Heterocyclic Carbenes 103</p> <p>4.4 Dissociative Substitution 105</p> <p>4.5 Associative Substitution 109</p> <p>4.6 Redox Effects and Interchange Substitution 111</p> <p>4.7 Photochemical Substitution 113</p> <p>4.8 Counterions and Solvents in Substitution 115</p> <p>References 116</p> <p>Problems 118</p> <p><b>5 Pi Complexes 121</b></p> <p>5.1 Alkene and Alkyne Complexes 121</p> <p>5.2 Allyl Complexes 126</p> <p>5.3 Diene Complexes 130</p> <p>5.4 Cyclopentadienyl Complexes 133</p> <p>5.5 Arenes and Other Alicyclic Ligands 140</p> <p>5.6 Metalacycles 143</p> <p>5.7 Stability of Polyene and Polyenyl Complexes 144</p> <p>References 145</p> <p>Problems 145</p> <p><b>6 Oxidative Addition and Reductive Elimination 147</b></p> <p>6.1 Introduction 147</p> <p>6.2 Concerted Additions 149</p> <p>6.3 S<sub>N</sub>2 Pathways 152</p> <p>6.4 Radical Mechanisms 153</p> <p>6.5 Ionic Mechanisms 155</p> <p>6.6 Reductive Elimination 156</p> <p>6.7 Sigma Bond Metathesis 162</p> <p>6.8 Ligand-Assisted 1,2-Additions and Eliminations 163</p> <p>6.9 Oxidative Coupling 164</p> <p>6.10 Proton-Coupled Electron Transfer 165</p> <p>References 166</p> <p>Problems 167</p> <p><b>7 Insertion and Elimination 169</b></p> <p>7.1 Introduction 169</p> <p>7.2 1,1-Insertion 171</p> <p>7.3 1,2-Insertion 175</p> <p>7.4 Outer Sphere Insertions 179</p> <p>7.5 α-,β-,γ- and δ-Elimination 180</p> <p>References 182</p> <p>Problems 182</p> <p><b>8 Addition and Abstraction 185</b></p> <p>8.1 Introduction 185</p> <p>8.2 Nucleophilic Addition to CO 187</p> <p>8.3 Nucleophilic Addition to Polyenes and Polyenyls 189</p> <p>8.4 Nucleophilic Abstraction 196</p> <p>8.5 Electrophilic Addition and Abstraction 197</p> <p>8.6 Single-Electron Transfer and Radical Reactions 200</p> <p>References 201</p> <p>Problems 202</p> <p><b>9 Homogeneous Catalysis 205</b></p> <p>9.1 Catalytic Cycles 205</p> <p>9.2 Alkene Isomerization 211</p> <p>9.3 Hydrogenation 213</p> <p>9.4 Alkene Hydroformylation 221</p> <p>9.5 Alkene Hydrocyanation 223</p> <p>9.6 Alkene Hydrosilylation 224</p> <p>9.7 Coupling Reactions 225</p> <p>9.8 Organometallic Oxidation Catalysis 227</p> <p>9.9 Electrocatalysis 229</p> <p>9.10 Photoredox Catalysis 229</p> <p>9.11 Surface Supported Single-Atom and Cooperative Catalysis 231</p> <p>References 233</p> <p>Problems 235</p> <p><b>10 Physical Methods 239</b></p> <p>10.1 Mechanism 239</p> <p>10.2 <sup>1</sup>H NMR Spectroscopy 240</p> <p>10.3 <sup>13</sup>C NMR Spectroscopy 243</p> <p>10.4 <sup>31</sup>P NMR Spectroscopy 244</p> <p>10.5 Dynamic NMR 246</p> <p>10.6 Spin Saturation Transfer 249</p> <p>10.7 <i>T</i><sub>1</sub> and the Nuclear Overhauser Effect 250</p> <p>10.8 IR Spectroscopy 254</p> <p>10.9 Crystallography 256</p> <p>10.10 Electrochemistry and EPR 257</p> <p>10.11 Computation 259</p> <p>10.12 Other Methods 260</p> <p>References 262</p> <p>Problems 263</p> <p><b>11 M–L Multiple Bonds 265</b></p> <p>11.1 Carbenes 265</p> <p>11.2 Schrock Carbenes 272</p> <p>11.3 Carbynes 276</p> <p>11.4 Bridging Carbenes and Carbynes 278</p> <p>11.5 <i>N</i>-Heterocyclic Carbenes 279</p> <p>11.6 Multiple Bonds to Heteroatoms 282</p> <p>References 285</p> <p>Problems 286</p> <p><b>12 Metathesis Polymerization and Bond Activation 289</b></p> <p>12.1 Alkene Metathesis 289</p> <p>12.2 Alkene Dimerization, Oligomerization, and Polymerization 295</p> <p>12.3 Activation of CO and CO<sub>2</sub> 301</p> <p>12.4 C−H Activation 305</p> <p>12.5 Dehydrogenative Oxidation and Hydrogen Borrowing 309</p> <p>References 311</p> <p>Problems 313</p> <p><b>13 Green Energy and Materials Applications 317</b></p> <p>13.1 Green Chemistry 317</p> <p>13.2 Energy Chemistry 320</p> <p>13.3 Clusters and Nanoparticles 323</p> <p>13.4 Organometallic Materials 325</p> <p>References 332</p> <p>Problems 334</p> <p><b>14 Organic Applications 337</b></p> <p>14.1 Carbon–Carbon and Carbon–Heteroatom Coupling 338</p> <p>14.2 Metathesis 343</p> <p>14.3 Cyclopropanation and C–H Insertion 345</p> <p>14.4 Hydrogenation 346</p> <p>14.5 Carbonylation 348</p> <p>14.6 Oxidation 350</p> <p>14.7 C–H Activation 352</p> <p>14.8 Click Chemistry and Cycloaddition 355</p> <p>14.9 Photoredox Catalysis 356</p> <p>References 359</p> <p>Problems 360</p> <p><b>15 Paramagnetic and High-Oxidation-State Complexes 363</b></p> <p>15.1 Magnetism and Spin States 364</p> <p>15.2 Cyclopentadienyl Complexes 371</p> <p>15.3 f-Block Complexes 373</p> <p>References 380</p> <p>Problems 381</p> <p><b>16 Bioorganometallic Chemistry 383</b></p> <p>16.1 Introduction 384</p> <p>16.2 Coenzyme B<sub>12</sub> 388</p> <p>16.3 Nitrogen Fixation 394</p> <p>16.4 Nickel Enzymes 402</p> <p>16.5 Artificial Enzymes 407</p> <p>16.6 Biomedical and Biocatalytic Applications 407</p> <p>References 410</p> <p>Problems 412</p> <p>Appendix A: Useful Texts on Allied Topics 415</p> <p>Appendix B: Major Reaction Types 419</p> <p>Solutions to Problems 421</p> <p>Index 437</p>
<p><b>Robert H. Crabtree F.R.S.</b> is Whitehead Professor of Chemistry at Yale, a Fellow of the Royal Society and of the American Chemical Society, and a member of the American Academy and of the National Academy of Sciences.
<p><b>Provides vital information on organometallic compounds, their preparation, and use in synthesis, and explores the fundamentals of the field and its modern applications</b> <p>Fully updated and expanded to reflect recent advances, the new, seventh edition of this bestselling text presents students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. Increased focus is given to organic synthesis applications, nanoparticle science, and green chemistry. This edition features up-to-date examples of fundamental reaction steps and greater emphasis on key topics like oxidation catalysis, CH functionalization, nanoclusters and nanoparticles, and green chemistry. New coverage is added for computational chemistry, energy production, and biochemical aspects of organometallic chemistry. <p><i>The Organometallic Chemistry of the Transition Metals, Seventh Edition</i> provides new/enhanced chapter coverage of ligand-assisted additions and eliminations; proton-coupled electron transfer; surface, supported, and cooperative catalysis; green, energy, and materials applications; and photoredox catalysis. It covers coordination chemistry; alkyls and hydrides; Pi-complexes; and oxidative addition and reductive elimination. The book also features sections on insertion and elimination; spectroscopy; metathesis polymerization and bond activation; and more. <ul> <li>Provides an excellent foundation of the fundamentals of organometallic chemistry</li> <li>Includes end-of-chapter problems and their solutions</li> <li>Expands and includes up-to-date examples of fundamental reaction steps and focuses on important topics such as oxidation catalysis, CH functionalization, nanoparticles, and green chemistry</li> <li>Features all new coverage for computational chemistry, energy production, and biochemical aspects of organometallic chemistry</li> </ul> <p><i>The Organometallic Chemistry of the Transition Metals, Seventh Edition</i> is an insightful book that will appeal to all advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry, as well as any practicing chemist in those fields.

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