Orbital Interaction Theory of Organic Chemistry

366 Pages·2000·7.21 MB·english

by  Rauk A.

OrbitalInteractionTheoryofOrganicChemistry,SecondEdition.ArviRauk
Copyright(2001JohnWiley&Sons,Inc.
ISBNs:0-471-35833-9(Hardback);0-471-22041-8(Electronic)
OrbitalInteractionTheoryofOrganicChemistry,SecondEdition.ArviRauk
Copyright(2001JohnWiley&Sons,Inc.
ISBNs:0-471-35833-9(Hardback);0-471-22041-8(Electronic)
ORBITAL INTERACTION
THEORY OF ORGANIC
CHEMISTRY
Second Edition
ORBITAL INTERACTION
THEORY OF ORGANIC
CHEMISTRY
Second Edition
ARVI RAUK
ProfessorEmeritus
Universityof Calgary, Canada
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CONTENTS
PREFACE xiii
1 SYMMETRY AND STEREOCHEMISTRY 1
Purpose / 1
DefinitionofaGroup / 2
MolecularPointGroups / 2
SchoenfliesNotation / 2
InterrelationsofSymmetryElements / 3
TypeClassification / 3
IsomerismandMeasurements / 6
StereoisomerismofMolecules / 8
StereotopicRelationshipsofGroupsinMolecules / 9
AsymmetricSynthesisandStereochemistry / 10
NMRandStereochemistry / 12
SymmetryandStructuralParameters / 14
NoteonHybridization / 15
SymmetryandOrbitals / 16
AtomicOrbitals / 16
MolecularandGroupOrbitals / 17
InWhatCombination? / 19
2 MOLECULAR ORBITAL THEORY 20
Introduction / 20
ElectronicSchro¨dingerEquation(A.1) / 21
v
vi CONTENTS
FockEquations(A.42) / 23
TheBasisSet(STO-3G,6-31G*,andAllThat) / 24
OrbitalEnergiesandOrbitals / 25
RepresentationofMOs / 27
TotalEnergiesandtheHartree–FockLimit / 29
SuccessesandFailuresofHartree–FockTheory / 29
BeyondHartree–Fock / 30
DensityFunctionalTheory / 31
GeometryOptimization / 31
NormalCoordinatesandHarmonicFrequencyAnalysis / 32
ZeroPointVibrationalEnergies / 33
3 ORBITAL INTERACTION THEORY 34
RelationshiptoHartree–FockEquations / 34
Hu¨ckelApproximation / 34
OrbitalEnergiesandTotalElectronicEnergy / 34
CaseStudyofaTwo-OrbitalInteraction / 35
Case1:e (cid:136)e ,S (cid:136)0 / 38
A B AB
Case2:e (cid:136)e ,S >0,S f1 / 39
A B AB AB
Case3:e >e ,S (cid:136)0 / 40
A B AB
Case4:e >e ,S >0 / 42
A B AB
E¤ectofOverlap / 44
EnergeticE¤ectofOverlap / 44
OrbitalE¤ectofOverlap / 44
FirstLookatBonding / 45
RelationshiptoPerturbationTheory / 45
GeneralizationsforIntermolecularInteractions / 46
EnergyandChargeDistributionChangesfromOrbitalInteraction / 47
Four-Electron,Two-OrbitalInteraction / 47
Three-Electron,Two-OrbitalInteraction / 48
Two-Electron,Two-OrbitalInteraction / 49
One-Electron,Two-OrbitalInteraction / 51
Zero-Electron,Two-OrbitalInteraction / 51
InteractionsbetweenMolecules:ManyElectrons,ManyOrbitals / 52
GeneralPrinciplesGoverningtheMagnitudeofh andS / 52
AB AB
InteractionsofMOs / 52
ElectrostaticE¤ects / 55
GroupOrbitals / 56
Zero-CoordinatedAtoms / 56
MonocoordinatedAtoms / 57
DicoordinatedAtoms / 58
TricoordinatedAtoms / 59
TetracoordinatedAtoms / 59
CONTENTS vii
AssumptionsforApplicationofQualitativeMOTheory / 61
Example:CarbonylGroup / 62
ConstructionofInteractionDiagram / 62
InterpretationofInteractionDiagram / 65
ChemicalReactivity / 66
WhyDoesItWorkandWhenMightitNot? / 69
4 SIGMA BONDS AND ORBITAL INTERACTION THEORY 72
C—XsBonds:X(cid:136)C,N,O,FandX(cid:136)F,Cl,Br,I / 72
sBonds:HomolyticversusHeterolyticCleavage / 74
HeterolyticCleavageofsBondsInvolvingCorH / 74
HomolyticCleavageofsBondsInvolvingCorH / 75
HomonuclearsBondsC—C,N—N,O—O,F—F,Cl—Cl,
Br—Br,andI—I / 76
InteractionsofsBonds / 77
sBondsasElectronDonorsorAcceptors / 81
sBondsasElectronAcceptors / 81
AsasAcceptor / 81
AsapAcceptor / 82
sBondsasElectronDonors / 83
AsasDonor / 83
AsapDonor / 84
BondinginCyclopropane / 84
5 SIMPLE HU¨CKEL MOLECULAR ORBITAL THEORY 86
SimpleHu¨ckelAssumptions / 86
ChargeandBondOrderinSHMOTheory:(S (cid:136)0,OneOrbitalper
AB
Atom) / 91
ElectronPopulationandNetChargeofCenterA / 91
BondOrderbetweenCentersAandB / 92
FactorsGoverningEnergiesofMOs:SHMOTheory / 92
ReferenceEnergyandEnergyScale / 92
HeteroatomsinSHMOTheory / 93
E¤ectofCoordinationNumberonaandb / 93
HybridizationatCinTermsofaandb / 96
GrossClassificationofMoleculesontheBasisofMOEnergies / 96
6 REACTIONS AND PROPERTIES OF pBONDS 98
ReactionsofOlefins(Alkenes) / 98
E¤ectofX:Substituents / 99
E¤ectofZSubstituents / 101
E¤ectof‘‘C’’Substituents / 101
E¤ectofDistortionofMolecularSkeleton / 102
viii CONTENTS
Alkynes / 103
pBondstoandbetweenHigherRowElements / 103
pBondstoSilicon,Phosphorus,andSulfur / 103
7 REACTIVE INTERMEDIATES 105
.
ReactiveIntermediates[CH ](cid:135),[CH ](cid:255),[CH ],and[:CH ] / 105
3 3 3 2
Carbocations / 105
IntermolecularReactionsofCarbocations / 106
IntramolecularReactionsofCarbocations / 107
SilylCations / 108
Carbanions / 108
CarbonFreeRadicals / 110
Carbenes / 114
NitrenesandNitreniumIons / 116
Nitrenes / 116
NitreniumIons / 118
8 CARBONYL COMPOUNDS 121
ReactionsofCarbonylCompounds / 121
ElectrophilicAttackonaCarbonylGroup / 121
BasicityandNucleophilicityoftheOxygenAtom / 122
NucleophilicAttackonaCarbonylGroup / 124
AmideGroup / 126
ThermodynamicStabilityofSubstitutedCarbonylGroups / 127
9 NUCLEOPHILIC SUBSTITUTION REACTIONS 129
NucleophilicSubstitutionatSaturatedCarbon / 129
UnimolecularNucleophilicSubstitutionS 1 / 129
N
BimolecularNucleophilicSubstitutionS 2 / 130
N
AnotherDescriptionoftheS 2Reaction:VBCMModel / 134
N
10 BONDS TO HYDROGEN 137
HydrogenBondsandProtonAbstractionReactions / 137
HydrogenBonds / 137
SymmetricalandBifurcatedHydrogenBonds / 139
ProtonAbstractionReactions / 141
E2EliminationReaction / 143
E1cBMechanismReaction / 144
E1EliminationReaction / 144
ReactionwithElectrophiles:HydrideAbstractionandHydride
Bridging / 145
ActivationbypDonors(X:and‘‘C’’Substituents) / 145
CONTENTS ix
HydrideAbstraction / 145
HydrideBridges / 147
ReactionwithFreeRadicals:HydrogenAtomAbstractionandOne-or
Three-ElectronBonding / 147
Hydrogen-BridgedRadicals / 147
HydrogenAtomTransfer / 148
11 AROMATIC COMPOUNDS 150
ReactionsofAromaticCompounds / 150
CyclicpSystemsbySimpleHu¨ckelMOTheory / 150
Aromaticityins-BondedArrays? / 151
ReactionsofSubstitutedBenzenes / 152
ElectrophilicSubstitutions / 152
E¤ectofSubstituentsonSubstrateReactivity / 153
ElectrophilicAttackonX:-SubstitutedBenzenes / 153
ElectrophilicAttackonZ-SubstitutedBenzenes / 154
ElectrophilicAttackon‘‘C’’-SubstitutedBenzenes / 155
ElectrophilicAttackonNAromatics:PyrroleandPyridine / 155
NucleophilicSubstitutions / 157
E¤ectofSubstituentsonSubstrateReactivity / 158
NucleophilicAttackonZ-SubstitutedBenzenes / 158
NucleophilicAttackonNAromatics:PyrroleandPyridine / 158
NucleophilicSubstitutionbyProtonAbstraction / 159
12 PERICYCLIC REACTIONS 161
GeneralConsiderations / 161
CycloadditionsandCycloreversions / 162
StereochemicalConsiderations / 162
ElectrocyclicReactions / 165
StereochemicalConsiderations / 165
CheletropicReactions / 165
StereochemicalConsiderations / 165
SigmatropicRearrangements / 166
StereochemicalConsiderations / 166
ComponentAnalysis(AllowedorForbidden?) / 167
RuleforComponentAnalysis / 168
Diels–AlderReaction / 169
CopeRearrangement / 170
1,3-DipolarCycloadditionReactions / 171
13 ORGANOMETALLIC COMPOUNDS 175
TransitionMetals / 175
x CONTENTS
LigandsinTransitionMetalComplexes / 176
OrbitalsinTransitionMetalBonding / 176
OrbitalEnergies / 178
ValenceOrbitalsofReactiveMetalComplexes / 179
SixValenceOrbitalsofTricoordinatedMetal / 182
FiveValenceOrbitalsofTetracoordinatedMetal / 182
FourValenceOrbitalsofPentacoordinatedStructure / 185
TransitionMetalsandC—HorH—HSigmaBonds / 186
MoreAboutCLigandsinTransitionMetalComplexes / 186
ChelatingLigands / 187
Organicp-BondedMoleculesasLigands / 187
TransitionMetalBondingtoAlkenes:Zeise’sSalt / 187
AgosticInteraction / 191
Ziegler–NattaPolymerization / 192
OxidativeAdditiontoH—HandC—HBonds / 194
14 ORBITAL AND STATE CORRELATION DIAGRAMS 196
GeneralPrinciples / 196
Woodward–Ho¤manOrbitalCorrelationDiagrams / 197
CycloadditionReactions / 197
ElectrocyclicReactions / 198
CheletropicReactions / 201
PhotochemistryfromOrbitalCorrelationDiagrams / 201
LimitationsofOrbitalCorrelationDiagrams / 203
StateCorrelationDiagrams / 203
ElectronicStatesfromMOs / 205
RulesforCorrelationofElectronicStates / 206
Example:CarbeneAdditiontoanOlefin / 206
15 PHOTOCHEMISTRY 209
Photoexcitation / 209
JablonskiDiagram / 210
FateofExcitedMoleculeinSolution / 211
Dauben–Salem–TurroAnalysis / 212
NorrishTypeIIReactionofCarbonylCompounds / 213
NorrishTypeICleavageReactionofCarbonylCompounds / 215
APPENDIX A: DERIVATION OF HARTREE–FOCK THEORY 218
ElectronicHamiltonianOperator / 218
ElectronicSchro¨dingerEquation / 220
ExpectationValues / 221
Many-ElectronWaveFunction / 221