Lewis Basicity and Affinity Scales: Data and Measurement

490 Pages·2010·5.44 MB·English

by  Christian Laurence

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Lewis Basicity and Affinity Scales
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Lewis Basicity and
Affinity Scales
Data and Measurement
CHRISTIAN LAURENCE
De´partementdeChimie,Universite´ deNantes–CNRS,France
JEAN-FRANC¸OIS GAL
InstitutdeChimie,Universite´ deNice-SophiaAntipolis–CNRS,France
A John Wiley and Sons, Ltd., Publication
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Thiseditionfirstpublished2010
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LibraryofCongressCataloging-in-PublicationData
Laurence,Christian.
Lewisbasicityandaffinityscales:dataandmeasurement/ChristianLaurence,Jean-Franc¸oisGal.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-74957-9
1.Acids–Basicity. I.Gal,Jean-Franc¸ois. II.Title.
QD477.L382009
546(cid:2).24–dc22 2009030807
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
ISBN9780470749579
Typesetin10/12ptTimesbyAptaraInc.,NewDelhi,India.
PrintedandboundinGreatBritainbyCPIAntonyRowe,Chippenham,Wiltshire
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To
Eliane
Vale´rie,Anne
Hugo,Cle´ment,SimonandLouis
C.Laurence
Inmemoryofmymother
whoenabledme tofulfillmyvocationasaresearcher
J.-F.Gal
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Contents
Preface pageix
1 LewisBasicityandAffinityMeasurement:DefinitionsandContext 1
1.1 TheBro¨nstedDefinitionofAcidsandBases 2
1.2 ScalesofBro¨nstedBasicityandAffinityinSolution 3
1.3 ScalesofBro¨nstedBasicityandAffinityintheGasPhase 6
1.4 TheLewisDefinitionofAcidsandBases 6
1.5 QuantumChemicalDescriptionsofLewisAcid/BaseComplexes 10
1.5.1 Valence-BondModel 10
1.5.2 PerturbationMolecularOrbitalTheory 10
1.5.3 VariationalSupermolecularMethodandEnergy
DecompositionSchemes 12
1.5.4 NaturalBondOrbitalTheory 17
1.5.5 QuantumTheoryofAtomsinMolecules 18
1.6 MeasurementofLewisBasicity 20
1.6.1 Gas-phaseReactions 21
1.6.2 SolutionReactions 22
1.6.3 StandardStateTransformations 23
1.6.4 ChoiceofSolvent 24
1.7 MeasurementofLewisAffinity 24
1.8 TheRoleoftheSolvent 29
1.9 SpectroscopicScalesofBasicity(Affinity) 34
1.10 PolybasicCompounds 38
1.11 AttemptsataQuantitativeFormulationoftheLewisDefinition
ofAcidsandBases 42
1.11.1 HardandSoftAcidsandBases 42
1.11.2 TheECWandECTModels 47
1.11.3 TheBetaandXiEquation 52
1.11.4 AChemometricApproach 53
1.11.5 QuantumChemicalDescriptorsforBasicityScales 56
1.12 ConcludingRemarksandContentofChapters2–7 58
References 60
2 TheDonorNumberorSbCl AffinityScale 71
5
2.1 StructureofSbCl Complexes 71
5
2.2 DefinitionoftheDonorNumberScale 73
2.3 ExperimentalDeterminationoftheDonorNumber 73
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2.4 TheDonorNumberScale:Data 74
2.5 CriticalDiscussion 80
References 81
3 TheBF AffinityScale 85
3
3.1 StructureofBF Complexes 86
3
3.2 DefinitionoftheBF AffinityScale 88
3
3.3 ExperimentalDeterminationoftheBF AffinityScale 89
3
3.4 TheBF AffinityScale:Data 90
3
3.5 Discussion 102
3.5.1 MediumEffects 102
3.5.2 HardnessofBF 102
3
3.5.3 ComparisonoftheBF andSbCl AffinityScales 103
3 5
3.5.4 ComputationoftheBF Affinity 104
3
3.6 Conclusion 105
References 106
4 ThermodynamicandSpectroscopicScalesofHydrogen-Bond
BasicityandAffinity 111
4.1 StructureofHydrogen-BondedComplexes 113
4.2 Hydrogen-BondBasicityScales:EarlyWorks 117
4.3 The4-FluorophenolHydrogen-BondBasicityScale 119
4.3.1 Definition 119
4.3.2 MethodofDetermination 119
4.3.3 PolyfunctionalHydrogen-BondAcceptors 120
4.3.4 Data 121
4.3.5 RangeofValidityoftheScale 167
4.4 Hydrogen-BondAffinityScales:EarlyStudies 168
4.5 The4-FluorophenolAffinityScale 170
4.6 Comparisonof4-FluorophenolAffinityandBasicityScales 185
4.7 SpectroscopicScales 188
4.7.1 InfraredShiftofMethanol 188
4.7.2 SolvatochromicShiftsof4-Nitrophenoland4-Nitroaniline 210
4.8 Conclusion 221
References 221
5 ThermodynamicandSpectroscopicScalesofHalogen-Bond
BasicityandAffinity 229
5.1 StructureofHalogen-BondedComplexes 231
5.2 TheDiiodineBasicityScale 237
5.2.1 DefinitionoftheScale 237
5.2.2 MethodsfortheDeterminationofDiiodine
ComplexationConstants 238
5.2.3 TemperatureCorrection 239
5.2.4 SolventEffects 239
5.2.5 Data 243