Organo Main Group Chemistry

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.

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