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 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
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