Arrow Pushing in Inorganic Chemistry : a Logical Approach to the Chemistry of the Main Group Elements

347 Pages·2014·15.98 MB·English

by  Abhik Ghosh

Arrow Pushing in
Inorganic Chemistry

Arrow Pushing in
Inorganic Chemistry
A Logical Approach to the Chemistry
of the Main-Group Elements
Abhik Ghosh
Steffen Berg
Copyright©2014byJohnWiley&Sons,Inc.Allrightsreserved
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ISBN:978-1-118-17398-5
PrintedintheUnitedStatesofAmerica
10987654321
Contents
FOREWORD xi
PREFACE xiii
ACKNOWLEDGMENTS xvii
1. ACollectionofBasicConcepts 1
1.1 NucleophilesandElectrophiles:TheSN2Paradigm 2
1.2 WhatMakesforaGoodNucleophile? 5
1.3 HardandSoftAcidsandBases:TheHSABPrinciple 8
1.4 pKaValues:WhatMakesforaGoodLeavingGroup? 9
1.5 RedoxPotentials 11
1.6 ThermodynamicControl:BondDissociationEnergies(BDEs) 11
1.7 Bimolecular𝛽-Elimination(E2) 14
1.8 ProtonTransfers(PTs) 15
1.9 ElementaryAssociativeandDissociativeProcesses(AandD) 16
1.10 Two-StepIonicMechanisms:TheSN2-SiPathway 19
1.11 Two-StepIonicMechanisms:TheSN1andE1Pathways 20
1.12 ElectrophilicAdditiontoCarbon–CarbonMultipleBonds 22
1.13 ElectrophilicSubstitutiononAromatics:Addition–Elimination 23
1.14 NucleophilicAdditiontoCarbon–HeteroatomMultipleBonds 24
1.15 CarbanionsandRelatedSyntheticIntermediates 26
1.16 Carbenes 29
1.17 OxidativeAdditionsandReductiveEliminations 30
Sectionsmarkedwithanasterisk(*)maybeskippedonfirstreading.
v
vi CONTENTS
1.18 Migrations 32
1.19 LigandExchangeReactions 33
1.20 RadicalReactions 35
1.21 PericyclicReactions 37
1.22 ArrowPushing:OrganicParadigms 38
1.23 InorganicArrowPushing:ThinkingLikeaLonePair 38
1.24 Definitions:Valence,OxidationState,FormalCharge,andCoordination
Number 40
1.25 ElementsofBondinginHypervalentCompounds 41
1.26 The𝜆Convention 45
1.27 TheInertPairEffect 46
1.28 Summary 47
FurtherReading 48
2. Thes-BlockElements:AlkaliandAlkalineEarthMetals 50
2.1 Solubility 51
2.2 Thes-BlockMetalsasReducingAgents 52
2.3 ReductiveCouplings 53
2.4 DissolvingMetalReactions 56
2.5 OrganolithiumandOrganomagnesiumCompounds 58
2.6 DihydrogenActivationbyFrustratedLewisPairs(FLPs) 61
I I
2.7 AMg –Mg Bond 63
2.8 Summary 64
FurtherReading 65
3. Group13Elements 66
3.1 Group13CompoundsasLewisAcids 67
3.2 Hydroboration 70
3.3 Group13-BasedReducingAgents 73
3.4 FromBorazinetoGalliumArsenide:13–15Compounds 76
3.5 Low-Oxidation-StateCompounds 80
3.6 TheBorylAnion 87
3.7 Indium-MediatedAllylations 88
3.8 ThalliumReagents 89
3.9 Summary 94
FurtherReading 94
4. Group14Elements 96
4.1 SilylProtectingGroups 98
4.2 ACaseStudy:PetersonOlefination 103
4.3 Silanes 104
CONTENTS vii
4.4 The𝛽-SiliconEffect:Allylsilanes 106
4.5 SilylAnions 109
4.6 Organostannanes 112
4.7 Polystannanes 113
∗
4.8 CarbeneandAlkeneAnalogs 115
∗
4.9 AlkyneAnalogs 120
4.10 SilylCations 122
4.11 GlycolCleavagebyLeadTetraacetate 124
4.12 Summary 127
FurtherReading 128
5A. Nitrogen 129
5A.1 AmmoniaandSomeOtherCommonNitrogenNucleophiles 130
5A.2 SomeCommonNitrogenElectrophiles:Oxides,Oxoacids,
andOxoanions 131
5A.3 N–NBondedMolecules:SynthesisofHydrazine 133
5A.4 MultipleBondFormation:SynthesisofSodiumAzide 135
5A.5 ThermalDecompositionofNH NO andNH NO 137
4 2 4 3
5A.6 DiazoniumSalts 138
5A.7 AzoCompoundsandDiazene 140
∗
5A.8 IminesandRelatedFunctionalGroups:TheWolff–Kishner
ReductionandtheShapiroReaction 144
5A.9 DiazoCompounds 146
5A.10NitrenesandNitrenoids:TheCurtiusRearrangement 149
5A.11NitricOxideandNitrogenDioxide 151
5A.12Summary 155
FurtherReading 155
5B. TheHeavierPnictogens 156
5B.1 Oxides 158
5B.2 HalidesandOxohalides 160
5B.3 PhosphorusinBiology:WhyNatureChosePhosphate 163
5B.4 Arsenic-BasedDNA 166
5B.5 ArsenicToxicityandBiomethylation 168
5B.6 Alkali-InducedDisproportionationofPhosphorus 171
5B.7 DisproportionationofHypophosphorousAcid 173
5B.8 TheArbuzovReaction 175
5B.9 TheWittigandRelatedReactions:PhosphorusYlides 176
5B.10 Phosphazenes 180
∗
5B.11 TheCorey–WinterOlefination 185
5B.12 Triphenylphosphine-MediatedHalogenations 187
viii CONTENTS
∗
5B.13 TheMitsunobuReaction 188
∗
5B.14 TheVilsmeier–HaackReaction 191
5B.15 SbF andSuperacids 193
5
5B.16 BismuthinOrganicSynthesis:GreenChemistry 195
5B.17 Summary 200
FurtherReading 200
6. Group16Elements:TheChalcogens 202
6.1 TheDivalentState:FocusonSulfur 204
6.2 TheDivalentState:HydrogenPeroxide 205
6.3 S Cl andSCl 209
2 2 2
6.4 NucleophilicBreakdownofCyclopolysulfurRings 211
6.5 CyclooctachalcogenRingFormation 213
6.6 Higher-ValentStates:OxidesandOxoacids 215
6.7 SulfurOxochlorides 219
6.8 Ozone 222
6.9 SwernandRelatedOxidations 226
6.10 SulfurYlidesandSulfur-StabilizedCarbanions 228
∗
6.11 HydrolysisofS F :AMechanisticPuzzle 231
2 2
6.12 Higher-ValentSulfurFluorides 234
6.13 MartinSulfurane 236
6.14 Lawesson’sReagent 238
6.15 SulfurNitrides 240
∗
6.16 Selenium-MediatedOxidations 243
6.17 Higher-ValentTellurium:AMechanisticPuzzle 247
6.18 Summary 250
FurtherReading 251
7. TheHalogens 252
7.1 SomeNotesonElementalHalogens 254
7.2 Alkali-InducedDisproportionationofMolecularHalogens 258
7.3 Acid-InducedComproportionationofHalateandHalide 260
7.4 HypofluorousAcid,HOF 261
7.5 ElectrophilicFluorinatingAgents:N-FluoroCompounds 264
7.6 OxoacidsandOxoanions 268
7.7 HeptavalentChlorine 271
7.8 InterhalogenCompounds 275
∗
7.9 HalogensinOrganicSynthesis:SomeClassicalReactions 276
7.10 AnIntroductiontoHigher-ValentOrganoiodineCompounds 283
7.11 𝜆3-Iodanes 284
7.12 𝜆5-Iodanes:IBXandDess–MartinPeriodinane 288