Abhik Ghosh, Steffen Berg

Arrow Pushing in Inorganic Chemistry

A Logical Approach to the Chemistry of the Main-Group Elements

• Broschiertes Buch

Produktbeschreibung

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.

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.
- The first book to apply the arrow-pushing method to inorganic chemistry teaching
- 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
- Teaches students to recognize common inorganic species as electrophiles and nucleophiles, coupled with organic-style arrow-pushing
- Provides a degree of integration with what students learn in organic chemistry, facilitating learning of this subject
- Serves as an invaluable companion to any introductory inorganic chemistry textbook

Produktdetails

• Verlag: Wiley & Sons
• Artikelnr. des Verlages: 1W118173980
• 1. Auflage
• Seitenzahl: 352
• Erscheinungstermin: 18. August 2014
• Englisch
• Abmessung: 254mm x 178mm x 19mm
• Gewicht: 730g
• ISBN-13: 9781118173985
• ISBN-10: 1118173988
• Artikelnr.: 35452235

Autorenporträt

Steffen Berg and Abhik Ghosh 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.

Inhaltsangabe

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 beta-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 lambda 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 beta-Silicon Effect:
Allylsilanes 106 4.5 Silyl Anions 109 4.6 Organostannanes 112 4.7
Polystannanes 113 4.8* Carbene and Alkene Analogs 115 4.9* 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 NH4NO2 and
NH4NO3 137 5A.6 Diazonium Salts 138 5A.7 Azo Compounds and Diazene 140
5A.8* 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.11* The
Corey-Winter Olefination 185 5B.12 Triphenylphosphine-Mediated
Halogenations 187 5B.13* The Mitsunobu Reaction 188 5B.14* 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 6.11* 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 6.16* 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 7.9* Halogens in Organic Synthesis: Some
Classical Reactions 276 7.10 An Introduction to Higher-Valent Organoiodine
Compounds 283 7.11 lambda³-Iodanes 284 7.12 lambda^5-Iodanes: IBX and
Dess-Martin Periodinane 288 7.13 Periodic Acid Oxidations 290 7.14 Bromine
Trifluoride 291 7.15* Aryl-lambda³-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 321