Description
Book SynopsisThis 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.
Trade Review“Summing Up: Highly recommended. Chemistry libraries serving academic students at all levels, researchers/faculty, and professionals.” (Choice, 1 March 2012)
Table of ContentsPreface 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 α-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 π –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 σX−C / 46
2.8 Effect of σ ∗ X−C / 48
Notes 4: (σ, σ ∗) and (π, π ∗): 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
