Superacid Chemistry, Second Edition

866 Pages·2009·16.201 MB·English

by  George A. Olah, G. K. Surya Prakash, Arpad Molnar, Jean Sommer(auth.)

SUPERACID CHEMISTRY
SUPERACID CHEMISTRY
SECOND EDITION
George A. Olah
G. K. Surya Prakash
(cid:1) (cid:1) (cid:1)
Arpad Molnar
Jean Sommer
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LibraryofCongressCataloging-in-PublicationData:
Superacidchemistry/byGeorgeA.Olah...[etal.].–2nded.
p.cm.
Rev.ed.of:Superacids/GeorgeA.Olah,G.K.SuryaPrakash,JeanSommer.
c1985.
Includesindex.
ISBN978-0-471-59668-4(cloth)
1.Superacids.I.Olah,GeorgeA.(GeorgeAndrew),1927-II.Olah,
GeorgeA.(GeorgeAndrew),1927-Superacids.
QD477.O532009
5460.24–dc22
2008026776
PrintedintheUnitedStatesofAmerica
10987654321
InmemoryofKatherineBogdanovichLoker,BenefactorandFriend
CONTENTS
PrefacetotheSecondEdition xvii
PrefacetotheFirstEdition xix
1. GeneralAspects 1
1.1. DefiningAcidity 1
1.1.1. AcidsandBases 1
1.1.2. ThepHScale 3
1.1.3. AcidityFunctions 4
1.2. DefinitionofSuperacids 6
1.2.1. RangeofAcidities 7
1.3. TypesofSuperacids 9
1.3.1. PrimarySuperacids 10
1.3.2. BinarySuperacids 10
1.3.3. TernarySuperacids 10
1.3.4. SolidSuperacids 10
1.4. ExperimentalTechniquesforAcidityMeasurements
(ProticAcids) 11
1.4.1. SpectrophotometricMethod 11
1.4.2. NuclearMagneticResonanceMethods 13
1.4.2.1. ChemicalShiftMeasurements 15
1.4.2.2. ExchangeRateMeasurementsBased
onLine-ShapeAnalysis(DNMR:
DynamicNuclearMagneticResonance) 18
1.4.3. ElectrochemicalMethods 20
1.4.4. ChemicalKinetics 20
1.4.5. HeatsofProtonationofWeakBases 22
1.4.6. TheoreticalCalculationsandSuperacidity
intheGasPhase 22
1.4.7. EstimatingtheStrengthofLewisAcids 23
1.4.8. ExperimentalTechniquesAppliedtoSolidAcids 27
References 29
vii
viii CONTENTS
2. SuperacidSystems 35
2.1. PrimarySuperacids 35
2.1.1. BrønstedSuperacids 35
2.1.1.1 PerchloricAcid 35
2.1.1.2. ChlorosulfuricAcid 36
2.1.1.3. FluorosulfuricAcid 37
2.1.1.4. PerfluoroalkanesulfonicAcids 38
2.1.1.5. HydrogenFluoride 40
2.1.1.6. CarboraneSuperacidsH(CB HR X ) 41
11 5 6
2.1.2. LewisSuperacids 42
2.1.2.1. AntimonyPentafluoride 42
2.1.2.2. ArsenicPentafluoride 44
2.1.2.3. PhosphorusPentafluoride 44
2.1.2.4. TantalumandNiobiumPentafluoride 44
2.1.2.5. BoronTrifluoride 44
2.1.2.6. Tris(pentafluorophenyl)Borane 45
2.1.2.7. BoronTris(trifluoromethanesulfonate) 46
2.1.2.8. AproticOrganicSuperacids
(Vol’pin’sSystems) 46
2.2. BinarySuperacids 47
2.2.1. BinaryBrønstedSuperacids 47
2.2.1.1. HydrogenFluoride–FluorosulfuricAcid 47
2.2.1.2. HydrogenFluoride–Trifluoromethanesulfonic
Acid 47
2.2.1.3. Tetra(HydrogenSulfato)BoricAcid–Sulfuric
Acid 47
2.2.2. ConjugateBrønsted–LewisSuperacids 47
2.2.2.1. Oleums–PolysulfuricAcids 47
2.2.2.2. FluorosulfuricAcid–AntimonyPentafluoride
(‘‘MagicAcid’’) 49
2.2.2.3. FluorosulfuricAcid–SulfurTrioxide 53
2.2.2.4. HSO3F–MFn(SO3F)5(cid:1)n;n¼3,4,
M¼Nb,Ta 53
2.2.2.5. FluorosulfuricAcid–ArsenicPentafluoride 54
2.2.2.6. PerfluoroalkanesulfonicAcid–BasedSystems 54
2.2.2.7. HydrogenFluoride–AntimonyPentafluoride
(FluoroantimonicAcid) 56
2.2.2.8. HydrogenFluoride–PhosphorusPentafluoride 59
2.2.2.9. HydrogenFluoride–TantalumPentafluoride 60
CONTENTS ix
2.2.2.10. HydrogenFluoride–BoronTrifluoride
(TetrafluoroboricAcid) 60
2.2.2.11. ConjugateFriedel-CraftsAcids(HX–AlX ,etc.) 61
3
2.3. TernarySuperacids 62
2.3.1. HSO F–HF–SbF 62
3 5
2.3.2. HSO F–HF–CF SO H 63
3 3 3
2.3.3. CF SO H–HF–LewisAcid 63
3 3
2.3.4. HSO F–SbF –SO 63
3 5 3
2.4. SolidSuperacids 63
2.4.1. ZeoliticAcids 64
2.4.2. PolymericResinSulfonicAcids 65
2.4.2.1. LewisAcid-ComplexedSulfonicAcidResins 65
2.4.2.2. PerfluorinatedPolymerResinAcids 66
2.4.3. EnhancedAciditySolids 68
2.4.3.1. BrønstedAcid-ModifiedMetalOxides:
TiO –H SO ;ZrO –H SO 68
2 2 4 2 2 4
2.4.3.2. LewisAcid-ModifiedMetalOxides
andMixedOxides 69
2.4.3.3. LewisAcid-ComplexedMetalSalts 70
2.4.4. ImmobilizedSuperacids(BoundtoInertSupports) 71
2.4.4.1. SuperacidsImmobilizedonSolidSupports 71
2.4.4.2. Graphite-IntercalatedSuperacids 72
2.4.4.3. SbF -FluorinatedGraphite,
5
SbF -FluorinatedAl O 74
5 2 3
References 75
3. CarbocationsinSuperacidSystems 83
3.1. Introduction 83
3.1.1. DevelopmentoftheCarbocationConcept:Early
KineticandStereochemicalStudies 83
3.1.2. ObservationofStable,Long-LivedCarbocations 84
3.1.3. GeneralConceptofCarbocations 85
3.2. MethodsofGeneratingCarbocationsinSuperacidsSystems 87
3.3. MethodsandTechniquesintheStudyofCarbocations 88
3.3.1. NuclearMagneticResonanceSpectrainSolution 88
3.3.2. 13CNMRChemicalShiftAdditivity 89
3.3.3. IsotopicPerturbationTechnique 90
3.3.4. Solid-State13CNMR 90
3.3.5. X-rayDiffraction 91
x CONTENTS
3.3.6. ToolofIncreasingElectronDemand 91
3.3.7. CoreElectronSpectroscopy 91
3.3.8. InfraredandRamanSpectroscopy 92
3.3.9. ElectronicSpectroscopy 92
3.3.10. Low-TemperatureSolutionCalorimetricStudies 92
3.3.11. QuantumMechanicalCalculations 93
3.4. TrivalentCarbocations 93
3.4.1. AlkylCations 93
3.4.1.1. EarlyUnsuccessfulAttempts 93
3.4.1.2. PreparationfromAlkylFluorides
inAntimonyPentafluorideSolution
andSpectroscopicStudies 94
3.4.1.3. PreparationfromOtherPrecursors 108
3.4.1.4. ObservationinDifferentSuperacids 112
3.4.2. CycloalkylCations 112
3.4.3. BridgeheadCations 116
3.4.4. CyclopropylmethylCations 120
3.4.5. AlkenylCations 123
3.4.6. AlkadienylandPolyenylicCations 125
3.4.7. AreniumIons 126
3.4.8. EthyleneareniumIons 132
3.4.9. PropargylandAllenylmethylCations
(MesomericVinylCations) 134
3.4.10. ThePhenylCation 139
3.4.11. ArylmethylandAlkylarylmethylCations 140
3.4.12. CarbodicationsandPolycations 147
3.4.13. AromaticStabilizedCationsandDications 157
3.4.14. PolycyclicAreneDications 162
3.4.15. FullereneCations 164
3.4.16. Heteroatom-StabilizedCations 167
3.4.16.1. HalogenasHeteroatom 167
3.4.16.2. OxygenasHeteroatom 172
3.4.16.3. SulfurasHeteroatom 192
3.4.16.4. NitrogenasHeteroatom 195
3.4.17. CarbocationsComplexedtoMetalAtoms 204
3.5. Equilibrating(Degenerate)andHigher(FiveorSix)
Coordinate(Nonclassical)Carbocations 206
3.5.1. AlkoniumIons(ProtonatedAlkanesCnH2nþ3þ) 206
3.5.1.1. TheMethoniumIon(CH þ) 207
5
CONTENTS xi
3.5.1.2. MultiplyProtonatedMethaneIons
andTheirAnalogs 212
3.5.1.3. VariedMethaneCations 214
þ
3.5.1.4. EthoniumIon(C H )andAnalogs 216
2 7
3.5.1.5. ProponiumIonsandAnalogs 218
3.5.1.6. HigherAlkoniumIons 219
3.5.1.7. AdamantoniumIons 224
3.5.2. EquilibratingandBridgedCarbocations 225
3.5.2.1. Degenerate1,2-ShiftsinCarbocations 225
3.5.2.2. The2-NorbornylCation 229
3.5.2.3. The7-NorbornylCation 239
3.5.2.4. The2-Bicyclo[2.1.1]hexylCation 240
3.5.2.5. DegenerateCyclopropylmethyland
CyclobutylCations 241
3.5.2.6. ShiftstoDistantCarbons 246
3.5.2.7. 9-Barbaralyl(Tricyclo[3.3.1.02,8]nona-3,
6-dien-9-yl)CationsandBicyclo[3.2.2]
nona-3,6,8-trien-2-ylCations 253
3.5.2.8. The1,3,5,7-Tetramethyl-and1,2,3,5,
7-Pentamethyl-2-adamantylCations 257
3.5.3. HomoaromaticCations 258
3.5.3.1. MonohomoaromaticCations 259
3.5.3.2. BishomoaromaticCations 260
3.5.3.3. TrishomoaromaticCations 265
3.5.3.4. Three-DimensionalHomoaromaticity 266
3.5.4. PyramidalCations 267
þ
3.5.4.1. (CH) -TypeCations 267
5
3.5.4.2. (CH) 2þ-TypeDications 270
6
References 273
4. HeterocationsinSuperacidSystems 311
4.1. Introduction 311
4.2. OniumIons 311
4.2.1. OxoniumIons 311
þ
4.2.1.1. HydroniumIon(H O ) 311
3
þ
4.2.1.2. PrimaryOxoniumIons[ROH ] 313
2
4.2.1.3. SecondaryOxoniumIons[RR0OHþ] 319
4.2.1.4. TertiaryOxoniumIons 322
4.2.1.5. AuratedOxoniumIons 328
xii CONTENTS
þ
4.2.1.6. HydrogenPeroxoniumIon(H O )
3 2
andDerivatives 329
þ
4.2.1.7. OzoniumIon(HO ) 330
3
4.2.2. SulfoniumIons 331
þ
4.2.2.1. HydrosulfoniumIon(H S ) 331
3
4.2.2.2. PrimarySulfoniumIons 332
4.2.2.3. SecondarySulfoniumIons 334
4.2.2.4. TertiaryAlkyl(Aryl)SulfoniumIons 335
4.2.2.5. HalosulfoniumIons 340
4.2.2.6. SulfoniumIonswithOtherHeteroligands 342
4.2.3. SelenoniumandTelluroniumIons 350
4.2.3.1. HydridoselenoniumandHydridotelluroniumIons 350
4.2.3.2. AcidicSelenoniumandTelluroniumIons 351
4.2.3.3. TertiarySelenoniumandTelluroniumIons 352
4.2.3.4. HaloselenoniumandHalotelluroniumIons 356
4.2.3.5. AuratedSelenoniumandTelluroniumIons 357
4.2.3.6. PolychalcogenDications 358
4.2.4. HaloniumIons 360
4.2.4.1. Acyclic(Open-Chain)HaloniumIons 362
4.2.4.2. CyclicHaloniumIons 372
4.2.5. OniumIonsofGroup15Elements 381
4.2.5.1. 2-AzoniaalleneandDerivedCations 381
4.2.5.2. DiazoniumIons 383
þ
4.2.5.3. NitroniumIon(NO ) 390
2
þ
4.2.5.4. NitrosoniumIon(NO ) 392
4.2.5.5. Ammonium,Phosphonium,Arsonium,
andStiboniumIons 394
4.3. EniumIons 397
4.3.1. EniumIonsofGroup13Elements 397
4.3.1.1. BoreniumIons 397
4.3.1.2. AlumeniumIons 400
4.3.2. EniumIonsofGroup14Elements 401
4.3.2.1. SiliceniumIons 401
4.3.2.2. GermeniumIons 411
4.3.2.3. EniumIonsofOtherGroup14Elements 413
4.3.3. EniumIonsofGroup15Elements 415
4.3.3.1. NitreniumIons 415
4.3.3.2. PhospheniumIons 417
4.3.3.3. EniumIonsofOtherGroup15Elements 423