This vital resource book captures the essential scope of organic chemistry of all main group elements and covers all main group elements dealing with syntheses and reactions of their organic compounds. While organic compounds of second row elements centered at carbon are the major components of animals and plants, those of the third row and below are also important and have unique roles which this book discusses. Since main group chemistry has been traditionally classified as a part of inorganic chemistry, this book establishes the scope of organic chemistry of main group elements.
This vital resource book captures the essential scope of organic chemistry of all main group elements and covers all main group elements dealing with syntheses and reactions of their organic compounds. While organic compounds of second row elements centered at carbon are the major components of animals and plants, those of the third row and below are also important and have unique roles which this book discusses. Since main group chemistry has been traditionally classified as a part of inorganic chemistry, this book establishes the scope of organic chemistry of main group elements.
KIN-YA AKIBA, PHD, is a Professor Emeritus in the Department of Chemistry at Hiroshima University and a visiting researcher at the Advanced Research Institute for Science and Engineering at Waseda University. Among his many honors are the 1996 Humboldt Research Award, the 1997 Award by the Chemical Society of Japan, and the 2000 Medal with Purple Ribbon by the Prime Minister of Japan.
Inhaltsangabe
Preface ix 1 Main Group Elements and Heteroatoms: Scope and Characteristics 1 1.1 Aufbau Principle and Sign of Orbitals 1 1.2 Electronic Configuration of an Atom: Main Group Elements and Heteroatoms 3 1.3 Fundamental Properties of Main Group Elements 5 1.4 Acidity of Carboxylic Acid and Substituent Effect 7 1.5 Heteroatom Effect 10 1.5.1 Stabilization of ±-Carbocation by Resonance: Stereoelectronic Effect 10 1.5.2 Coordination with Lewis Acids 15 References 16 Notes 1: Electronegativity 17 Notes 2: Importance of Formal Logic-I: Oxidation Number and Formal Charge 19 Notes 3: Importance of Formal Logic-II: Octet Rule, Eighteen-Electron Rule, Hypervalence 23 2 Main Group Element Effect 25 2.1 What Is Main Group Element Effect? 25 2.2 Single Bond Energy and À -Bond Energy 27 2.3 Hypervalent Compound 31 2.4 Effect of Hypervalent Bond (1): 3c-4e Bond and Structure 33 2.5 Effect of Hypervalent Bond (2): Apicophilicity and Pseudorotation 41 2.6 Effect of Hypervalent Bond (3): Ligand Coupling Reaction (LCR) and Edge Inversion 45 2.7 Effect of ÃX-C 46 2.8 Effect of à * X-C 48 Notes 4: (Ã, à *) and (À, À *): HMO (Hueckel Molecular Orbital) and Electrocyclic Reaction 57 3 Lithium, Magnesium, and Copper Compounds 63 3.1 Synthesis 64 3.2 Structure 66 3.3 Reaction 68 3.3.1 Deprotonation as Base 69 3.3.2 Nucleophilic Reaction 72 3.3.3 Conjugate Addition of Lithium Dimethylcuprate 76 References 77 4 Boron and Aluminum Compounds 79 4.1 Synthesis 80 4.2 Structure 82 4.3 Reaction 84 References 88 5 Silicon, Tin, and Lead Compounds 91 5.1 Synthesis 92 5.2 Reaction 94 5.3 Organotin and Lead Compounds 100 References 104 Notes 5: Stable Carbene and Its Complex 105 6 Phosphorus, Antimony, and Bismuth Compounds 111 6.1 Phosphorus Compounds 112 6.2 Synthesis of Organophosphorus Compounds 113 6.3 Tertiary Phosphine and Its Nucleophilic Reaction 115 6.4 Arbuzov Reaction 117 6.5 Perkow Reaction 118 6.6 Synthesis of Optically Active Phosphines 119 6.7 Ylide and Wittig Reaction and Related Ones 123 6.8 Reactions of Phosphonium Salts and Formation of Phosphoranes 131 6.9 Freezing BPR and Its Effect 138 6.10 Antimony and Bismuth Compounds 143 References 146 Notes 6: Dreams of Staudinger and Wittig 149 Notes 7: Stereochemistry in Nucleophilic Substitution of MX4-type Compounds: Inversion or Retention 155 7 Sulfur, Selenium, and Tellurium Compounds 159 7.1 Sulfur Compounds 160 7.2 Synthesis of Organosulfur Compounds 160 7.3 Reactions of Organosulfur Compounds 166 7.4 Structure and Reaction of Hypervalent Organosulfur Compounds 170 7.5 Selenium and Tellurium Compounds 175 References 178 Notes 8: Inversion Mechanism of NH3 and NF3: Vertex Inversion or Edge Inversion 181 8 Organohalogen Compounds: Fluorine and Iodine Compounds 187 8.1 Synthesis of Chlorine and Bromine Compounds 188 8.2 Fluorine Compounds 190 8.3 Iodine Compounds 195 References 199 9 Atrane and Transannular Interaction: Formation of Hypervalent Bond 201 9.1 Introduction 201 9.2 Silatrane and Atrane 202 9.3 Transannular Interaction (1) 208 9.4 Transannular Interaction (2) 210 References 211 10 Unsaturated Compounds of Main Group Elements of Third Period and Heavier 213 10.1 Introduction 213 10.2 Unsaturated Bonds of Group 15 Elements of Third Period and Heavier 215 10.3 Unsaturated Bonds of Group 14 Elements of Third Period and Heavier 219 10.4 Aromatic Compounds of Group 14 Elements 222 References 223 11 Ligand Coupling Reaction 225 11.1 Introduction 225 11.2 Selectivity of Ligand Coupling Reaction: Theoretical Investigation 226 11.3 Ligand Coupling Reaction of Organic Compounds of Phosphorus, Antimony, and Bismuth 227 11.4 Ligand Coupling Reaction of Organic Compounds of Sulfur, Selenium, and Tellurium 237 11.5 Ligand Coupling Reaction of Organoiodine Compounds 241 References 245 Notes 9: Hexavalent Organotellurium Compounds 247 12 Hypervalent Carbon Compounds: Can Hexavalent Carbon Exist? 251 12.1 Introduction 251 12.2 Attempts for Pentacoordinate Hypervalent Carbon Species 253 12.3 Synthesis of Pentacoordinate Hypervalent Carbon Species (10-C-5) and Bond Switching at Carbon and Boron 254 12.4 Attempts to Hexacoordinate Hypervalent Carbon Species (12-C-6) 259 References 262 Notes 10: Main Group Element Porphyrins 265 Index 269
Preface ix 1 Main Group Elements and Heteroatoms: Scope and Characteristics 1 1.1 Aufbau Principle and Sign of Orbitals 1 1.2 Electronic Configuration of an Atom: Main Group Elements and Heteroatoms 3 1.3 Fundamental Properties of Main Group Elements 5 1.4 Acidity of Carboxylic Acid and Substituent Effect 7 1.5 Heteroatom Effect 10 1.5.1 Stabilization of ±-Carbocation by Resonance: Stereoelectronic Effect 10 1.5.2 Coordination with Lewis Acids 15 References 16 Notes 1: Electronegativity 17 Notes 2: Importance of Formal Logic-I: Oxidation Number and Formal Charge 19 Notes 3: Importance of Formal Logic-II: Octet Rule, Eighteen-Electron Rule, Hypervalence 23 2 Main Group Element Effect 25 2.1 What Is Main Group Element Effect? 25 2.2 Single Bond Energy and À -Bond Energy 27 2.3 Hypervalent Compound 31 2.4 Effect of Hypervalent Bond (1): 3c-4e Bond and Structure 33 2.5 Effect of Hypervalent Bond (2): Apicophilicity and Pseudorotation 41 2.6 Effect of Hypervalent Bond (3): Ligand Coupling Reaction (LCR) and Edge Inversion 45 2.7 Effect of ÃX-C 46 2.8 Effect of à * X-C 48 Notes 4: (Ã, à *) and (À, À *): HMO (Hueckel Molecular Orbital) and Electrocyclic Reaction 57 3 Lithium, Magnesium, and Copper Compounds 63 3.1 Synthesis 64 3.2 Structure 66 3.3 Reaction 68 3.3.1 Deprotonation as Base 69 3.3.2 Nucleophilic Reaction 72 3.3.3 Conjugate Addition of Lithium Dimethylcuprate 76 References 77 4 Boron and Aluminum Compounds 79 4.1 Synthesis 80 4.2 Structure 82 4.3 Reaction 84 References 88 5 Silicon, Tin, and Lead Compounds 91 5.1 Synthesis 92 5.2 Reaction 94 5.3 Organotin and Lead Compounds 100 References 104 Notes 5: Stable Carbene and Its Complex 105 6 Phosphorus, Antimony, and Bismuth Compounds 111 6.1 Phosphorus Compounds 112 6.2 Synthesis of Organophosphorus Compounds 113 6.3 Tertiary Phosphine and Its Nucleophilic Reaction 115 6.4 Arbuzov Reaction 117 6.5 Perkow Reaction 118 6.6 Synthesis of Optically Active Phosphines 119 6.7 Ylide and Wittig Reaction and Related Ones 123 6.8 Reactions of Phosphonium Salts and Formation of Phosphoranes 131 6.9 Freezing BPR and Its Effect 138 6.10 Antimony and Bismuth Compounds 143 References 146 Notes 6: Dreams of Staudinger and Wittig 149 Notes 7: Stereochemistry in Nucleophilic Substitution of MX4-type Compounds: Inversion or Retention 155 7 Sulfur, Selenium, and Tellurium Compounds 159 7.1 Sulfur Compounds 160 7.2 Synthesis of Organosulfur Compounds 160 7.3 Reactions of Organosulfur Compounds 166 7.4 Structure and Reaction of Hypervalent Organosulfur Compounds 170 7.5 Selenium and Tellurium Compounds 175 References 178 Notes 8: Inversion Mechanism of NH3 and NF3: Vertex Inversion or Edge Inversion 181 8 Organohalogen Compounds: Fluorine and Iodine Compounds 187 8.1 Synthesis of Chlorine and Bromine Compounds 188 8.2 Fluorine Compounds 190 8.3 Iodine Compounds 195 References 199 9 Atrane and Transannular Interaction: Formation of Hypervalent Bond 201 9.1 Introduction 201 9.2 Silatrane and Atrane 202 9.3 Transannular Interaction (1) 208 9.4 Transannular Interaction (2) 210 References 211 10 Unsaturated Compounds of Main Group Elements of Third Period and Heavier 213 10.1 Introduction 213 10.2 Unsaturated Bonds of Group 15 Elements of Third Period and Heavier 215 10.3 Unsaturated Bonds of Group 14 Elements of Third Period and Heavier 219 10.4 Aromatic Compounds of Group 14 Elements 222 References 223 11 Ligand Coupling Reaction 225 11.1 Introduction 225 11.2 Selectivity of Ligand Coupling Reaction: Theoretical Investigation 226 11.3 Ligand Coupling Reaction of Organic Compounds of Phosphorus, Antimony, and Bismuth 227 11.4 Ligand Coupling Reaction of Organic Compounds of Sulfur, Selenium, and Tellurium 237 11.5 Ligand Coupling Reaction of Organoiodine Compounds 241 References 245 Notes 9: Hexavalent Organotellurium Compounds 247 12 Hypervalent Carbon Compounds: Can Hexavalent Carbon Exist? 251 12.1 Introduction 251 12.2 Attempts for Pentacoordinate Hypervalent Carbon Species 253 12.3 Synthesis of Pentacoordinate Hypervalent Carbon Species (10-C-5) and Bond Switching at Carbon and Boron 254 12.4 Attempts to Hexacoordinate Hypervalent Carbon Species (12-C-6) 259 References 262 Notes 10: Main Group Element Porphyrins 265 Index 269
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