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Arrow Pushing in Inorganic Chemistry

A Logical Approach to the Chemistry of the Main Group Elements
BuchKartoniert, Paperback
352 Seiten
Englisch
Wiley & Sonserschienen am16.09.20141. Auflage
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.mehr
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Produkt

KlappentextInvolved 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.
Details
ISBN/GTIN978-1-118-17398-5
ProduktartBuch
EinbandartKartoniert, Paperback
Erscheinungsjahr2014
Erscheinungsdatum16.09.2014
Auflage1. Auflage
Seiten352 Seiten
SpracheEnglisch
Gewicht726 g
Artikel-Nr.17831301

Inhalt/Kritik

Inhaltsverzeichnis
Foreword xi Preface xiii Acknowledgments xvii 1. A Collection of Basic Concepts 1 1.1 Nucleophiles and Electrophiles: The SN2 Paradigm 2 1.2 What Makes for a Good Nucleophile? 5 1.3 Hard and Soft Acids and Bases: The HSAB Principle 8 1.4 pKa Values: What Makes for a Good Leaving Group? 9 1.5 Redox Potentials 11 1.6 Thermodynamic Control: Bond Dissociation Energies (BDEs) 11 1.7 Bimolecular β-Elimination (E2) 14 1.8 Proton Transfers (PTs) 15 1.9 Elementary Associative and Dissociative Processes (A and D) 16 1.10 Two-Step Ionic Mechanisms: The SN2-Si Pathway 19 1.11 Two-Step Ionic Mechanisms: The SN1 and E1 Pathways 20 1.12 Electrophilic Addition to Carbon-Carbon Multiple Bonds 22 1.13 Electrophilic Substitution on Aromatics: Addition-Elimination 23 1.14 Nucleophilic Addition to Carbon-Heteroatom Multiple Bonds 24 1.15 Carbanions and Related Synthetic Intermediates 26 1.16 Carbenes 29 1.17 Oxidative Additions and Reductive Eliminations 30 1.18 Migrations 32 1.19 Ligand Exchange Reactions 33 1.20 Radical Reactions 35 1.21 Pericyclic Reactions 37 1.22 Arrow Pushing: Organic Paradigms 38 1.23 Inorganic Arrow Pushing: Thinking Like a Lone Pair 38 1.24 Definitions: Valence, Oxidation State, Formal Charge, and Coordination Number 40 1.25 Elements of Bonding in Hypervalent Compounds 41 1.26 The λ Convention 45 1.27 The Inert Pair Effect 46 1.28 Summary 47 Further Reading 48 2. The s-Block Elements: Alkali and Alkaline Earth Metals 50 2.1 Solubility 51 2.2 The s-Block Metals as Reducing Agents 52 2.3 Reductive Couplings 53 2.4 Dissolving Metal Reactions 56 2.5 Organolithium and Organomagnesium Compounds 58 2.6 Dihydrogen Activation by Frustrated Lewis Pairs (FLPs) 61 2.7 A MgI -MgI Bond 63 2.8 Summary 64 Further Reading 65 3. Group 13 Elements 66 3.1 Group 13 Compounds as Lewis Acids 67 3.2 Hydroboration 70 3.3 Group 13-Based Reducing Agents 73 3.4 From Borazine to Gallium Arsenide: 13-15 Compounds 76 3.5 Low-Oxidation-State Compounds 80 3.6 The Boryl Anion 87 3.7 Indium-Mediated Allylations 88 3.8 Thallium Reagents 89 3.9 Summary 94 Further Reading 94 4. Group 14 Elements 96 4.1 Silyl Protecting Groups 98 4.2 A Case Study: Peterson Olefination 103 4.3 Silanes 104 4.4 The β-Silicon Effect: Allylsilanes 106 4.5 Silyl Anions 109 4.6 Organostannanes 112 4.7 Polystannanes 113 4.8â Carbene and Alkene Analogs 115 4.9â Alkyne Analogs 120 4.10 Silyl Cations 122 4.11 Glycol Cleavage by Lead Tetraacetate 124 4.12 Summary 127 Further Reading 128 5A. Nitrogen 129 5A.1 Ammonia and Some Other Common Nitrogen Nucleophiles 130 5A.2 Some Common Nitrogen Electrophiles: Oxides, Oxoacids, and Oxoanions 131 5A.3 N-N Bonded Molecules: Synthesis of Hydrazine 133 5A.4 Multiple Bond Formation: Synthesis of Sodium Azide 135 5A.5 Thermal Decomposition of NH4NO 2 and NH4NO 3 137 5A.6 Diazonium Salts 138 5A.7 Azo Compounds and Diazene 140 5A.8 â Imines and Related Functional Groups: The Wolff-Kishner Reduction and the Shapiro Reaction 144 5A.9 Diazo Compounds 146 5A.10 Nitrenes and Nitrenoids: The Curtius Rearrangement 149 5A.11 Nitric Oxide and Nitrogen Dioxide 151 5A.12 Summary 155 Further Reading 155 5B. The Heavier Pnictogens 156 5B.1 Oxides 158 5B.2 Halides and Oxohalides 160 5B.3 Phosphorus in Biology: Why Nature Chose Phosphate 163 5B.4 Arsenic-Based DNA 166 5B.5 Arsenic Toxicity and Biomethylation 168 5B.6 Alkali-Induced Disproportionation of Phosphorus 171 5B.7 Disproportionation of Hypophosphorous Acid 173 5B.8 The Arbuzov Reaction 175 5B.9 The Wittig and Related Reactions: Phosphorus Ylides 176 5B.10 Phosphazenes 180 5B.11â The Corey-Winter Olefination 185 5B.12 Triphenylphosphine-Mediated Halogenations 187 5B.13â The Mitsunobu Reaction 188 5B.14â The Vilsmeier-Haack Reaction 191 5B.15 SbF5 and Superacids 193 5B.16 Bismuth in Organic Synthesis: Green Chemistry 195 5B.17 Summary 200 Further Reading 200 6. Group 16 Elements: The Chalcogens 202 6.1 The Divalent State: Focus on Sulfur 204 6.2 The Divalent State: Hydrogen Peroxide 205 6.3 S2Cl2 and SCl2 209 6.4 Nucleophilic Breakdown of Cyclopolysulfur Rings 211 6.5 Cyclooctachalcogen Ring Formation 213 6.6 Higher-Valent States: Oxides and Oxoacids 215 6.7 Sulfur Oxochlorides 219 6.8 Ozone 222 6.9 Swern and Related Oxidations 226 6.10 Sulfur Ylides and Sulfur-Stabilized Carbanions 228 6.11â Hydrolysis of S2F2: A Mechanistic Puzzle 231 6.12 Higher-Valent Sulfur Fluorides 234 6.13 Martin Sulfurane 236 6.14 Lawesson´s Reagent 238 6.15 Sulfur Nitrides 240 6.16â Selenium-Mediated Oxidations 243 6.17 Higher-Valent Tellurium: A Mechanistic Puzzle 247 6.18 Summary 250 Further Reading 251 7. The Halogens 252 7.1 Some Notes on Elemental Halogens 254 7.2 Alkali-Induced Disproportionation of Molecular Halogens 258 7.3 Acid-Induced Comproportionation of Halate and Halide 260 7.4 Hypofluorous Acid, HOF 261 7.5 Electrophilic Fluorinating Agents: N-Fluoro Compounds 264 7.6 Oxoacids and Oxoanions 268 7.7 Heptavalent Chlorine 271 7.8 Interhalogen Compounds 275 7.9â Halogens in Organic Synthesis: Some Classical Reactions 276 7.10 An Introduction to Higher-Valent Organoiodine Compounds 283 7.11 λ3-Iodanes 284 7.12 λ5-Iodanes: IBX and Dess-Martin Periodinane 288 7.13 Periodic Acid Oxidations 290 7.14 Bromine Trifluoride 291 7.15â Aryl-λ3-Bromanes 294 7.16 Summary 298 Further Reading 299 8. The Noble Gases 300 8.1 The Xenon Fluorides: Fluoride Donors and Acceptors 302 8.2 O/F Ligand Exchanges 303 8.3 Xenon Fluorides as F+ Donors and Oxidants 304 8.4 Hydrolysis of XeF2 and XeF4 306 8.5 Xenate and Perxenate 307 8.6 Disproportionation of Xenate 308 8.7 Hydrolysis of XeF4 310 8.8 Other Compounds Containing Xe-O Bonds 311 8.9 Xe-N Bonds 312 8.10 Xe-C Bonds 313 8.11 Krypton Difluoride 314 8.12 Plus Ultra 316 8.13 Summary 316 Further Reading 316 Epilogue 318 Appendix A. Inorganic Chemistry Textbooks, with a Descriptive-Inorganic Focus 319 A.1 Introductory Texts 319 A.2 Advanced Texts 319 Appendix B. A Short List of Advanced Organic Chemistry Textbooks 320 Index 321mehr

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