Details

Arrow Pushing in Inorganic Chemistry


Arrow Pushing in Inorganic Chemistry

A Logical Approach to the Chemistry of the Main-Group Elements
1. Aufl.

von: Abhik Ghosh, Steffen Berg

63,99 €

Verlag: Wiley
Format: EPUB
Veröffentl.: 25.07.2014
ISBN/EAN: 9781118924532
Sprache: englisch
Anzahl Seiten: 352

DRM-geschütztes eBook, Sie benötigen z.B. Adobe Digital Editions und eine Adobe ID zum Lesen.

Beschreibungen

<p>Involved as it is with 95% of the periodic table, inorganic chemistry is one of the foundational subjects of scientific study. Inorganic catalysts are used in crucial industrial processes and the field, to a significant extent, also forms the basis of nanotechnology. Unfortunately, the subject is not a popular one for undergraduates. This book aims to take a step to change this state of affairs by presenting a mechanistic, logical introduction to the subject.</p> <p>Organic teaching places heavy emphasis on reaction mechanisms - "arrow-pushing" - and the authors of this book have found that a mechanistic approach works just as well for elementary inorganic chemistry. As opposed to listening to formal  lectures or learning the material by heart, by teaching students to recognize common inorganic species as electrophiles and nucleophiles, coupled with organic-style arrow-pushing, this book serves as a gentle and stimulating introduction to inorganic chemistry, providing students with the knowledge and opportunity to solve inorganic reaction mechanisms.<br /> • The first book to apply the arrow-pushing method to inorganic chemistry teaching<br /> • With the reaction mechanisms approach ("arrow-pushing"), students will no longer have to rely on memorization as a device for learning this subject, but will instead have a logical foundation for this area of study<br /> • Teaches students to recognize common inorganic species as electrophiles and nucleophiles, coupled with organic-style arrow-pushing<br /> • Provides a degree of integration with what students learn in organic chemistry, facilitating learning of this subject<br /> • Serves as an invaluable companion to any introductory inorganic chemistry textbook</p>
FOREWORD xi <p>PREFACE xiii</p> <p>ACKNOWLEDGMENTS xvii</p> <p><b>1. A Collection of Basic Concepts 1</b></p> <p>1.1 Nucleophiles and Electrophiles: The SN2 Paradigm 2</p> <p>1.2 What Makes for a Good Nucleophile? 5</p> <p>1.3 Hard and Soft Acids and Bases: The HSAB Principle 8</p> <p>1.4 pKa Values: What Makes for a Good Leaving Group? 9</p> <p>1.5 Redox Potentials 11</p> <p>1.6 Thermodynamic Control: Bond Dissociation Energies (BDEs) 11</p> <p>1.7 Bimolecular -Elimination (E2) 14</p> <p>1.8 Proton Transfers (PTs) 15</p> <p>1.9 Elementary Associative and Dissociative Processes (A and D) 16</p> <p>1.10 Two-Step Ionic Mechanisms: The SN2-Si Pathway 19</p> <p>1.11 Two-Step Ionic Mechanisms: The SN1 and E1 Pathways 20</p> <p>1.12 Electrophilic Addition to Carbon–Carbon Multiple Bonds 22</p> <p>1.13 Electrophilic Substitution on Aromatics: Addition–Elimination 23</p> <p>1.14 Nucleophilic Addition to Carbon–Heteroatom Multiple Bonds 24</p> <p>1.15 Carbanions and Related Synthetic Intermediates 26</p> <p>1.16 Carbenes 29</p> <p>1.17 Oxidative Additions and Reductive Eliminations 30</p> <p>1.18 Migrations 32</p> <p>1.19 Ligand Exchange Reactions 33</p> <p>1.20 Radical Reactions 35</p> <p>1.21 Pericyclic Reactions 37</p> <p>1.22 Arrow Pushing: Organic Paradigms 38</p> <p>1.23 Inorganic Arrow Pushing: Thinking Like a Lone Pair 38</p> <p>1.24 Definitions: Valence, Oxidation State, Formal Charge, and Coordination Number 40</p> <p>1.25 Elements of Bonding in Hypervalent Compounds 41</p> <p>1.26 The Convention 45</p> <p>1.27 The Inert Pair Effect 46</p> <p>1.28 Summary 47</p> <p>Further Reading 48</p> <p><b>2. The s-Block Elements: Alkali and Alkaline Earth Metals 50</b></p> <p>2.1 Solubility 51</p> <p>2.2 The s-Block Metals as Reducing Agents 52</p> <p>2.3 Reductive Couplings 53</p> <p>2.4 Dissolving Metal Reactions 56</p> <p>2.5 Organolithium and Organomagnesium Compounds 58</p> <p>2.6 Dihydrogen Activation by Frustrated Lewis Pairs (FLPs) 61</p> <p>2.7 A MgI–MgI Bond 63</p> <p>2.8 Summary 64</p> <p>Further Reading 65</p> <p><b>3. Group 13 Elements 66</b></p> <p>3.1 Group 13 Compounds as Lewis Acids 67</p> <p>3.2 Hydroboration 70</p> <p>3.3 Group 13-Based Reducing Agents 73</p> <p>3.4 From Borazine to Gallium Arsenide: 13–15 Compounds 76</p> <p>3.5 Low-Oxidation-State Compounds 80</p> <p>3.6 The Boryl Anion 87</p> <p>3.7 Indium-Mediated Allylations 88</p> <p>3.8 Thallium Reagents 89</p> <p>3.9 Summary 94</p> <p>Further Reading 94</p> <p><b>4. Group 14 Elements 96</b></p> <p>4.1 Silyl Protecting Groups 98</p> <p>4.2 A Case Study: Peterson Olefination 103</p> <p>4.3 Silanes 104</p> <p>4.4 The -Silicon Effect: Allylsilanes 106</p> <p>4.5 Silyl Anions 109</p> <p>4.6 Organostannanes 112</p> <p>4.7 Polystannanes 113</p> <p>4.8∗ Carbene and Alkene Analogs 115</p> <p>4.9∗ Alkyne Analogs 120</p> <p>4.10 Silyl Cations 122</p> <p>4.11 Glycol Cleavage by Lead Tetraacetate 124</p> <p>4.12 Summary 127</p> <p>Further Reading 128</p> <p><b>5A. Nitrogen 129</b></p> <p>5A.1 Ammonia and Some Other Common Nitrogen Nucleophiles 130</p> <p>5A.2 Some Common Nitrogen Electrophiles: Oxides, Oxoacids, and Oxoanions 131</p> <p>5A.3 N–N Bonded Molecules: Synthesis of Hydrazine 133</p> <p>5A.4 Multiple Bond Formation: Synthesis of Sodium Azide 135</p> <p>5A.5 Thermal Decomposition of NH4NO2 and NH4NO3 137</p> <p>5A.6 Diazonium Salts 138</p> <p>5A.7 Azo Compounds and Diazene 140</p> <p>5A.8∗ Imines and Related Functional Groups: The Wolff–Kishner Reduction and the Shapiro Reaction 144</p> <p>5A.9 Diazo Compounds 146</p> <p>5A.10 Nitrenes and Nitrenoids: The Curtius Rearrangement 149</p> <p>5A.11 Nitric Oxide and Nitrogen Dioxide 151</p> <p>5A.12 Summary 155</p> <p>Further Reading 155</p> <p><b>5B. The Heavier Pnictogens 156</b></p> <p>5B.1 Oxides 158</p> <p>5B.2 Halides and Oxohalides 160</p> <p>5B.3 Phosphorus in Biology: Why Nature Chose Phosphate 163</p> <p>5B.4 Arsenic-Based DNA 166</p> <p>5B.5 Arsenic Toxicity and Biomethylation 168</p> <p>5B.6 Alkali-Induced Disproportionation of Phosphorus 171</p> <p>5B.7 Disproportionation of Hypophosphorous Acid 173</p> <p>5B.8 The Arbuzov Reaction 175</p> <p>5B.9 The Wittig and Related Reactions: Phosphorus Ylides 176</p> <p>5B.10 Phosphazenes 180</p> <p>5B.11∗ The Corey–Winter Olefination 185</p> <p>5B.12 Triphenylphosphine-Mediated Halogenations 187</p> <p>5B.13∗ The Mitsunobu Reaction 188</p> <p>5B.14∗ The Vilsmeier–Haack Reaction 191</p> <p>5B.15 SbF5 and Superacids 193</p> <p>5B.16 Bismuth in Organic Synthesis: Green Chemistry 195</p> <p>5B.17 Summary 200</p> <p>Further Reading 200</p> <p><b>6. Group 16 Elements: The Chalcogens 202</b></p> <p>6.1 The Divalent State: Focus on Sulfur 204</p> <p>6.2 The Divalent State: Hydrogen Peroxide 205</p> <p>6.3 S2Cl2 and SCl2 209</p> <p>6.4 Nucleophilic Breakdown of Cyclopolysulfur Rings 211</p> <p>6.5 Cyclooctachalcogen Ring Formation 213</p> <p>6.6 Higher-Valent States: Oxides and Oxoacids 215</p> <p>6.7 Sulfur Oxochlorides 219</p> <p>6.8 Ozone 222</p> <p>6.9 Swern and Related Oxidations 226</p> <p>6.10 Sulfur Ylides and Sulfur-Stabilized Carbanions 228</p> <p>6.11∗ Hydrolysis of S2F2: A Mechanistic Puzzle 231</p> <p>6.12 Higher-Valent Sulfur Fluorides 234</p> <p>6.13 Martin Sulfurane 236</p> <p>6.14 Lawesson’s Reagent 238</p> <p>6.15 Sulfur Nitrides 240</p> <p>6.16∗ Selenium-Mediated Oxidations 243</p> <p>6.17 Higher-Valent Tellurium: A Mechanistic Puzzle 247</p> <p>6.18 Summary 250</p> <p>Further Reading 251</p> <p><b>7. The Halogens 252</b></p> <p>7.1 Some Notes on Elemental Halogens 254</p> <p>7.2 Alkali-Induced Disproportionation of Molecular Halogens 258</p> <p>7.3 Acid-Induced Comproportionation of Halate and Halide 260</p> <p>7.4 Hypofluorous Acid, HOF 261</p> <p>7.5 Electrophilic Fluorinating Agents: N-Fluoro Compounds 264</p> <p>7.6 Oxoacids and Oxoanions 268</p> <p>7.7 Heptavalent Chlorine 271</p> <p>7.8 Interhalogen Compounds 275</p> <p>7.9∗ Halogens in Organic Synthesis: Some Classical Reactions 276</p> <p>7.10 An Introduction to Higher-Valent Organoiodine Compounds 283</p> <p>7.11 3-Iodanes 284</p> <p>7.12 5-Iodanes: IBX and Dess–Martin Periodinane 288</p> <p>7.13 Periodic Acid Oxidations 290</p> <p>7.14 Bromine Trifluoride 291</p> <p>7.15∗ Aryl-3-Bromanes 294</p> <p>7.16 Summary 298</p> <p>Further Reading 299</p> <p><b>8. The Noble Gases 300</b></p> <p>8.1 The Xenon Fluorides: Fluoride Donors and Acceptors 302</p> <p>8.2 O/F Ligand Exchanges 303</p> <p>8.3 Xenon Fluorides as F+ Donors and Oxidants 304</p> <p>8.4 Hydrolysis of XeF2 and XeF4 306</p> <p>8.5 Xenate and Perxenate 307</p> <p>8.6 Disproportionation of Xenate 308</p> <p>8.7 Hydrolysis of XeF4 310</p> <p>8.8 Other Compounds Containing Xe–O Bonds 311</p> <p>8.9 Xe–N Bonds 312</p> <p>8.10 Xe–C Bonds 313</p> <p>8.11 Krypton Difluoride 314</p> <p>8.12 Plus Ultra 316</p> <p>8.13 Summary 316</p> <p>Further Reading 316</p> <p>Epilogue 318</p> <p>Appendix A. Inorganic Chemistry Textbooks, with a Descriptive-Inorganic Focus 319</p> <p>A.1 Introductory Texts 319</p> <p>A.2 Advanced Texts 319</p> <p>Appendix B. A Short List of Advanced Organic Chemistry Textbooks 320</p> <p>Index 321</p>
<p><b>Steffen Berg</b> and <b>Abhik Ghosh</b> are chemists based at UiT – The Arctic University of Norway. They share a passion for chemical education, and are particularly interested in developing methods to help high school students and undergraduates understand difficult concepts.</p>
<p><b>The first book to apply the arrow-pushing method to inorganic chemistry teaching</b></p> <p>… <i>It’s a real delight to see that this fundamental approach indeed works beautifully in inorganic chemistry. ... It makes one wonder why it hadn’t been “discovered’ sooner. –</i> Professor Carl C. Wamser, Portland State University.</p> <p>… <i>Students will learn where electrons want to go and their appreciation of how reactions occur will be greatly enhanced.</i> <i>… –</i> Professor John T. Groves, Princeton University</p> <p><i>I urge instructors to try the Ghosh-Berg method when faced with teaching the dreaded “descriptive” section of the inorganic course. Arrow pushing not only is great fun, students who try it may actually learn main group chemistry! –</i> Professor Harry Gray, California Institute of Technology</p> <p>Inorganic chemistry is a foundational subject of scientific study. However, the sheer size, encyclopedic presentation and memorization-heavy nature of typical textbooks have made it a formidable subject among undergraduates. Shifting gears by applying a mechanistic introduction to the subject, <i>Arrow-Pushing in Inorganic Chemistry: A Logical Approach to the Chemistry of the Main-Group Elements</i> provides students a gentle, logical and fun way to approach the vast body of facts that is inorganic chemistry.</p> <p>A valuable companion to any introductory inorganic chemistry textbook, <i>Arrow Pushing in Inorganic Chemistry</i>: <i>A Logical Approach to the Chemistry of the Main-Group Elements:</i></p> <p>Devotes one chapter to each group of the main-group elements</p> <ul> <li>Teaches students to recognize common inorganic species as electrophiles and nucleophiles, coupled with organic-style arrow-pushing</li> <li>Provides a high degree of integration with organic chemistry, thus helping students build on their prior knowledge</li> <li>Offers a stimulating mix of classic content and cutting-edge discoveries</li> </ul> <p>This excellent companion text makes inorganic chemistry more approachable and exciting for students. It's also ideal for professionals looking for an up-to-date refresher of the field and for scientists from other disciplines, including organic and physical chemists, biochemists, pharmaceutical scientists, physicists and engineers, who are new to the field.</p>

Diese Produkte könnten Sie auch interessieren:

Lanthanide and Actinide Chemistry
Lanthanide and Actinide Chemistry
von: Simon Cotton
PDF ebook
50,99 €
Mass Spectrometry of Inorganic and Organometallic Compounds
Mass Spectrometry of Inorganic and Organometallic Compounds
von: William Henderson, J. Scott McIndoe
PDF ebook
59,99 €
Neurodegenerative Diseases and Metal Ions, Volume 1
Neurodegenerative Diseases and Metal Ions, Volume 1
von: Astrid Sigel, Helmut Sigel, Roland K. O. Sigel
PDF ebook
228,99 €