Organo Main Group Chemistry

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