Spin States in Biochemistry and Inorganic Chemistry: Influence on Structure and Reactivity

472 Pages·2015·20.442 MB·English

by  Marcel Swart, Miquel Costas

Spin States in Biochemistry
and Inorganic Chemistry
Spin States in Biochemistry
and Inorganic Chemistry
Influence on Structure and Reactivity
Editedby
MARCELSWART
InstitutdeQu´ımicaComputacionaliCata`lisi&DepartamentdeQu´ımica,UniversitatdeGirona,Spain
and
Institucio´ CatalanadeRecercaiEstudisAvanc¸ats(ICREA),Barcelona,Spain
MIQUELCOSTAS
InstitutdeQu´ımicaComputacionaliCata`lisi&DepartamentdeQu´ımica,UniversitatdeGirona,Spain
Thiseditionfirstpublished2016
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LibraryofCongressCataloging-in-PublicationData
Spinstatesinbiochemistryandinorganicchemistry:influenceonstructureandreactivity/editedbyMarcelSwartandMiquelCostas.
pagescm
Includesbibliographicalreferencesandindex.
ISBN978-1-118-89831-4(cloth)
1.Nuclearspin. 2.Freeradicals(Chemistry) 3.Biochemistry. 4.Chemistry,Inorganic. I.Swart,Marcel,1971–editor. II.CostasSalgueiro,
Miquel,editor.
QP527.S652016
612′.01524–dc23
2015019422
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
ISBN:9781118898314
CoverImagesuppliedbyMarcelSwart.
Setin10/12ptTimesbyAptaraInc.,NewDelhi,India.
1 2016
VoorElviraenPoppy
PerlaJudit,laMireiail’Ariadna
Contents
AbouttheEditors xv
ListofContributors xvii
Foreword xxi
Acknowledgments xxiii
1 GeneralIntroductiontoSpinStates 1
MarcelSwartandMiquelCostas
1.1 Introduction 1
1.2 ExperimentalChemistry:Reactivity,SynthesisandSpectroscopy 2
1.3 ComputationalChemistry:QuantumChemistryandBasisSets 4
References 4
2 ApplicationofDensityFunctionalandDensityFunctionalBasedLigandFieldTheory
toSpinStates 7
ClaudeDaul,MatijaZlatar,MajaGruden-Pavlovic´ andMarcelSwart
2.1 Introduction 7
2.2 WhatIstheProblemwithTheory? 9
2.2.1 DensityFunctionalTheory 9
2.2.2 LFTheory:BridgingtheGapBetweenExperimentalandComputational
CoordinationChemistry 11
2.3 ValidationandApplicationStudies 15
2.3.1 UseofOPBE,SSB-DandS12gDensityFunctionalsforSpin-StateSplittings 17
2.3.2 ApplicationofLF-DFT 21
2.4 ConcludingRemarks 25
Acknowledgments 26
References 27
3 AbInitioWavefunctionApproachestoSpinStates 35
CarmenSousaandCoendeGraaf
3.1 IntroductionandScope 35
3.2 Wavefunction-BasedMethodsforSpinStates 35
3.2.1 SingleReferenceMethods 36
3.2.2 MultireferenceMethods 37
3.2.3 MRPerturbationTheory 39
3.2.4 VariationalApproaches 40
3.2.5 DensityMatrixRenormalizationGroupTheory 40
3.3 SpinCrossover 41
3.3.1 ChoiceofActiveSpaceandBasisSet 41
viii Contents
3.3.2 TheHS–LSEnergyDifference 43
3.3.3 Light-InducedExcitedSpinStateTrapping(LIESST) 45
3.3.4 SpinCrossoverinOtherMetals 47
3.4 MagneticCoupling 47
3.5 SpinStatesinBiochemicalandBiomimeticSystems 50
3.6 Two-StateReactivity 52
3.7 ConcludingRemarks 52
References 53
4 ExperimentalTechniquesforDeterminingSpinStates 59
CaroleDubocandMarcelloGennari
4.1 Introduction 59
4.2 MagneticMeasurements 61
4.2.1 g-AnisotropyandZero-FieldSplitting(zfs) 64
4.2.2 UnquenchedOrbitalMomentintheGroundState 64
4.2.3 ExchangeInteractions 64
4.2.4 SpinTransitionsandSpinCrossover 66
4.3 EPRSpectroscopy 66
4.4 Mo¨ssbauerSpectroscopy 70
4.5 X-raySpectroscopicTechniques 74
4.6 NMRSpectroscopy 77
4.7 OtherTechniques 80
4.A Appendix 81
4.A.1 TheoreticalBackground 81
4.A.2 ListofSymbols 82
References 82
5 MolecularDiscoveryinSpinCrossover 85
RobertJ.Deeth
5.1 Introduction 85
5.2 TheoreticalBackground 85
5.2.1 SpinTransitionCurves 88
5.2.2 Light-InducedExcitedSpinStateTrapping 89
5.3 ThermalSCOSystems:Fe(II) 90
5.4 SCOinNon-d6Systems 93
5.5 ComputationalMethods 95
5.6 Outlook 98
References 99
6 MultipleSpin-StateScenariosinOrganometallicReactivity 103
WojciechI.Dzik,WesleyBo¨hmerandBasdeBruin
6.1 Introduction 103
6.2 “Spin-Forbidden”ReactionsandTwo-StateReactivity 104
6.3 Spin-StateChangesinTransitionMetalComplexes 107
6.3.1 InfluenceoftheSpinStateontheKineticsofLigandExchange 108
6.3.2 StoichiometricBondMakingandBreakingReactions 109
6.3.3 Spin-StateSituationsInvolvingRedox-ActiveLigands 115
Contents ix
6.4 Spin-StateChangesinCatalysis 119
6.4.1 Catalytic(Cyclo)oligomerizations 119
6.4.2 PhillipsCr(II)/SiO Catalyst 121
2
6.4.3 SNS–CrCl Catalyst 123
3
6.5 ConcludingRemarks 125
References 126
7 PrinciplesandProspectsofSpin-StatesReactivityinChemistryandBioinorganic
Chemistry 131
DandamudiUsharani,BinjuWang,DinaA.SharonandSasonShaik
7.1 Introduction 131
7.2 Spin-StatesReactivity 132
7.2.1 Two-StateandMulti-StateReactivity 133
7.2.2 OriginsofSpin-SelectiveReactivity:Exchange-EnhancedReactivityandOrbital
SelectionRules 137
7.2.3 ConsiderationsofExchange-EnhancedReactivityversusOrbital-Controlled
Reactivity 140
7.2.4 ConsiderationofSpin-StateSelectivityinH-Abstraction:ThePowerofEER 142
7.2.5 TheOriginsofMechanisticSelection–WhyAreC–HHydroxylationsStepwise
Processes? 146
7.3 ProspectsofTwo-StateReactivityandMulti-StateReactivity 148
7.3.1 ProbingSpin-StateReactivity 148
7.3.2 AreSpinInversionProbabilitiesUsefulforAnalyzingTSR? 150
7.4 ConcludingRemarks 151
References 151
8 MultipleSpin-StateScenariosinGas-PhaseReactions 157
JanaRoithova´
8.1 Introduction 157
8.2 ExperimentalMethodsfortheInvestigationofMetal-IonReactions 158
8.3 MultipleStateReactivity:ReactionsofMetalCationswithMethane 160
8.4 EffectoftheOxidationState:ReactionsofMetalHydrideCationswithMethane 163
8.5 Two-StateReactivity:ReactionsofMetalOxideCations 164
8.6 EffectofLigands 171
8.7 EffectofNoninnocentLigands 174
8.8 ConcludingRemarks 177
References 178
9 CatalyticFunctionandMechanismofHemeandNonhemeIron(IV)–OxoComplexes
inNature 185
MatthewG.Quesne,AbayomiS.Faponle,DavidP.GoldbergandSamP.deVisser
9.1 Introduction 185
9.2 CytochromeP450Enzymes 186
9.2.1 ImportanceofCytochromeP450Enzymes 187
9.2.2 P450ActivationofLong-ChainFattyAcids 188
9.2.3 HemeMonooxygenasesandPeroxygenases 188
9.2.4 CatalyticCycleofCytochromeP450Enzymes 188
x Contents
9.3 NonhemeIronDioxygenases 190
9.3.1 CysteineDioxygenase 191
9.3.2 AlkBRepairEnzymes 192
9.3.3 NonhemeIronHalogenases 194
9.4 Conclusions 197
9.5 Acknowledgments 197
References 197
10 TerminalMetal–OxoSpecieswithUnusualSpinStates 203
SarahA.Cook,DavidC.LacyandAndyS.Borovik
10.1 Introduction 203
10.2 Bonding 204
10.2.1 BondingConsiderations:TetragonalSymmetry 204
10.2.2 BondingConsiderations:TrigonalSymmetry 205
10.2.3 MethodsofCharacterization 206
10.3 CaseStudies 206
10.3.1 Iron–OxoChemistry 206
10.3.2 Manganese–OxoChemistry 212
10.3.3 CautionaryTales:LateTransitionMetalOxidoComplexes 217
10.3.4 EffectsofRedoxInactiveMetalIons 217
10.3.5 Metal–OxylComplexes 218
10.4 Reactivity 218
10.4.1 GeneralConcepts:ProtonversusElectronTransfer 218
10.4.2 SpinStateandReactivity 220
10.5 Summary 220
References 221
11 MultipleSpinScenariosinTransition-MetalComplexesInvolvingRedox
Non-InnocentLigands 229
FlorianHeimsandKallolRay
11.1 Introduction 229
11.2 SurveyofNon-InnocentLigands 231
11.3 IdentificationofNon-InnocentLigands 232
11.3.1 X-rayCrystallography 232
11.3.2 EPRSpectroscopy 234
11.3.3 Mo¨ssbauerSpectroscopy 235
11.3.4 XASSpectroscopy 236
11.4 SelectedExamplesofBiologicalandChemicalSystemsInvolvingNon-InnocentLigands 237
11.4.1 Copper–RadicalInteraction 237
11.4.2 Iron–RadicalInteraction 246
11.5 ConcludingRemarks 252
References 253
12 MolecularMagnetism 263
GuillemArom´ı,PatrickGamezandOlivierRoubeau
12.1 Introduction 263
12.2 MolecularMagnetism:Motivations,EarlyAchievementsandFoundations 264
Contents xi
12.3 MolecularNanomagnets(MNM) 265
12.3.1 Single-MoleculeMagnets 266
12.3.2 Single-ChainMagnets(SCM) 268
12.3.3 Single-IonMagnets(SIM) 271
12.4 SwitchableSystems 273
12.4.1 SpinCrossover(SCO) 273
12.4.2 ValenceTautomerism(VT) 273
12.4.3 ChargeTransfer(CT) 275
12.4.4 Light-DrivenLigand-InducedSpinChange(LD-LISC) 276
12.4.5 Photoswitching(PS)ThroughIntermetallicCT 277
12.5 Molecular-BasedMagneticRefrigerants 278
12.5.1 TheMagneto-CaloricEffect,ItsExperimentalDeterminationandKeyParameters 278
12.5.2 MoleculartoExtendedFrameworkCoolersTowardsApplications 280
12.6 QuantumManipulationoftheElectronicSpinforQuantumComputing 282
12.6.1 OrganicRadicals 283
12.6.2 TransitionMetalClusters 284
12.6.3 LanthanidesasRealizationofQubits 285
12.6.4 EngineeringofMolecularQuantumGateswithLanthanideQubits 285
12.7 PerspectivesTowardApplicationsandConcludingRemarks 287
References 287
13 ElectronicStructure,Bonding,SpinCoupling,andEnergeticsofPolynuclearIron–Sulfur
Clusters–ABrokenSymmetryDensityFunctionalTheoryPerspective 297
KathrinH.Hopmann,VladimirPelmenschikov,Wen-GeHanDuandLouisNoodleman
13.1 Introduction 297
13.2 Iron–SulfurCoordination:GeometricandElectronicStructure 298
13.3 SpinPolarizationSplittingandtheInvertedLevelScheme 300
13.4 SpinCouplingandtheBrokenSymmetryMethod 300
13.5 ElectronLocalizationandDelocalization 301
13.6 PolynuclearSystems–CompetingHeisenbergInteractionsandSpin-Dependent
Delocalization 303
13.7 PreambletoThreeMajorTopics:Iron–Sulfur–Nitrosyls,Adenosine-5′-Phosphosulfate
Reductase,andtheProximalClusterofMembrane-Bound[NiFe]-Hydrogenase 303
13.7.1 NonhemeIronNitrosylComplexes 303
13.7.2 Adenosine-5′-PhosphosulfateReductase 310
13.7.3 ProximalClusterofO -TolerantMembrane-Bound[NiFe]-HydrogenaseinThree
2
RedoxStates 315
13.8 ConcludingRemarks 318
13.9 Acknowledgments 319
References 319
14 EnvironmentEffectsonSpinStates,Properties,andDynamicsfromMulti-level
QM/MMStudies 327
AlexanderPetrenkoandMatthiasStein
14.1 Introduction 327
14.1.1 EnvironmentalEffects 328
14.1.2 HybridQM/MMEmbeddingSchemes 329
xii Contents
14.2 TheQuantumSpinHamiltonian–LinkingTheoryandExperiment 332
14.3 TheSolventasanEnvironment 335
14.3.1 FourierTransformInfraredSpectroscopy 336
14.3.2 NuclearMagneticResonance 336
14.3.3 ElectronParamagneticResonance 336
14.4 EffectofDifferentLevelsofQMandMMTreatment 338
14.4.1 ConvergenceandCaveatsattheQMLevel 338
14.4.2 AccuracyoftheMMPart 341
14.4.3 QMversusQM/MMMethods 341
14.5 IllustrativeBioinorganicExamples 343
14.5.1 CytochromeP450 343
14.5.2 HydrogenaseEnzymes 349
14.5.3 PhotosystemIIandtheEffectofQMSize 354
14.6 FromStaticSpin-StatePropertiestoDynamicsandKineticsofElectronTransfer 357
14.7 FinalRemarksandConclusions 359
14.8 Acknowledgments 362
References 362
15 High-SpinandLow-SpinStatesin{FeNO}7,FeIV=O,andFeIII–OOHComplexes
andTheirCorrelationstoReactivity 369
EdwardI.Solomon,KyleD.SutherlinandMartinSrnec
15.1 Introduction 369
15.2 High-andLow-Spin{FeNO}7 Complexes:CorrelationstoO Activation 372
2
15.2.1 SpectroscopicDefinitionoftheElectronicStructureofHigh-Spin{FeNO}7 372
15.2.2 ComputationalStudiesofS=3/2{FeNO}7 ComplexesandRelated{FeO }8
2
Complexes 375
15.2.3 ExtensiontoIPNSandHPPD:ImplicationsforReactivity 377
15.2.4 Correlationto{FeNO}7 S=1/2 385
15.3 Low-Spin(S=1)andHigh-Spin(S=2)FeIV=OComplexes 386
15.3.1 FeIV=OS=1Complexes:𝜋∗FMO 386
15.3.2 FeIV=OS=2Sites:𝜋∗and𝜎∗FMOs 390
15.3.3 ContributionsofFMOstoReactivity 392
15.4 Low-Spin(S=1/2)andHigh-Spin(S=5/2)FeIII–OOHComplexes 396
15.4.1 SpinStateDependenceofO–OBondHomolysis 396
15.4.2 FeIII–OOHS=1/2Reactivity:ABLM 398
15.4.3 FeIII–OOHSpinState-DependentReactivity:FMOs 399
15.5 ConcludingRemarks 401
15.6 Acknowledgments 402
References 402
16 NMRAnalysisofSpinDensities 409
KaraL.Bren
16.1 IntroductionandScope 409
16.2 SpinDensityDistributioninTransitionMetalComplexes 410
16.3 NMRofParamagneticMolecules 412
16.3.1 ChemicalShifts 413
16.3.2 RelaxationRates 414