Page 9 - Arrow Pushing in Inorganic Chemistry A Logical Approach to the Chemistry of the Main Group Elements

CONTENTS vii
4.4 The -Silicon Effect: Allylsilanes 106
4.5 Silyl Anions 109
4.6 Organostannanes 112
4.7 Polystannanes 113
4.8 ∗ Carbene and Alkene Analogs 115
4.9 ∗ Alkyne Analogs 120
4.10 Silyl Cations 122
4.11 Glycol Cleavage by Lead Tetraacetate 124
4.12 Summary 127
Further Reading 128

5A. Nitrogen 129
5A.1 Ammonia and Some Other Common Nitrogen Nucleophiles 130
5A.2 Some Common Nitrogen Electrophiles: Oxides, Oxoacids,
and Oxoanions 131
5A.3 N–N Bonded Molecules: Synthesis of Hydrazine 133
5A.4 Multiple Bond Formation: Synthesis of Sodium Azide 135
5A.5 Thermal Decomposition of NH NO and NH NO 3 137
4
2
4
5A.6 Diazonium Salts 138
5A.7 Azo Compounds and Diazene 140
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5A.8 Imines and Related Functional Groups: The Wolff–Kishner
Reduction and the Shapiro Reaction 144
5A.9 Diazo Compounds 146
5A.10 Nitrenes and Nitrenoids: The Curtius Rearrangement 149
5A.11 Nitric Oxide and Nitrogen Dioxide 151
5A.12 Summary 155
Further Reading 155

5B. The Heavier Pnictogens 156
5B.1 Oxides 158
5B.2 Halides and Oxohalides 160
5B.3 Phosphorus in Biology: Why Nature Chose Phosphate 163
5B.4 Arsenic-Based DNA 166
5B.5 Arsenic Toxicity and Biomethylation 168
5B.6 Alkali-Induced Disproportionation of Phosphorus 171
5B.7 Disproportionation of Hypophosphorous Acid 173
5B.8 The Arbuzov Reaction 175
5B.9 The Wittig and Related Reactions: Phosphorus Ylides 176
5B.10 Phosphazenes 180
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5B.11 The Corey–Winter Olefination 185
5B.12 Triphenylphosphine-Mediated Halogenations 187