The Chemical Bond : Chemical Bonding Across the Periodic Table

568 Pages·2014·12 MB·English

by  Sason S

EditedbyGernotFrenkingand
SasonShaik
TheChemicalBond
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Edited by Gernot Frenking and Sason Shaik
The Chemical Bond
Chemical Bonding Across the Periodic Table
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V
Contents
Preface XV
ListofContributors XIX
1 ChemicalBondingofMain-GroupElements 1
MartinKaupp
1.1 IntroductionandDefinitions 1
1.2 TheLackofRadialNodesofthe2pShellAccountsforMostofthe
PeculiaritiesoftheChemistryofthe2p-Elements 2
1.2.1 HighElectronegativityandSmallSizeofthe2p-Elements 4
1.2.1.1 HybridizationDefects 4
1.2.2 TheInert-PairEffectanditsDependenceonPartialChargeofthe
CentralAtom 7
1.2.3 Stereo-ChemicallyActiveversusInactiveLonePairs 10
1.2.4 TheMultiple-BondParadigmandtheQuestionofBondStrengths 13
1.2.5 InfluenceofHybridizationDefectsonMagnetic-Resonance
Parameters 14
1.3 TheRoleoftheOuterd-OrbitalsinBonding 15
1.4 SecondaryPeriodicities:Incomplete-ScreeningandRelativistic
Effects 17
1.5 ‘‘Honoraryd-Elements’’:thePeculiaritiesofStructureandBondingof
theHeavyGroup2Elements 19
1.6 ConcludingRemarks 21
References 21
2 MultipleBondingofHeavyMain-GroupAtoms 25
GernotFrenking
2.1 Introduction 25
2.2 BondingAnalysisofDiatomicMoleculesE (E=N–Bi) 27
2
2.3 ComparativeBondingAnalysisofN andP withN andP 29
2 2 4 4
2.4 BondingAnalysisoftheTetrylynesHEEH(E=C–Pb) 32
VI Contents
2.5 ExplainingtheDifferentStructuresoftheTetrylynesHEEH
(E=C–Pb) 34
2.6 EnergyDecompositionAnalysisoftheTetrylynesHEEH
(E=C–Pb) 41
2.7 Conclusion 46
Acknowledgment 47
References 47
3 TheRoleofRecoupledPairBondinginHypervalentMolecules 49
DavidE.WoonandThomH.DunningJr.
3.1 Introduction 49
3.2 MultireferenceWavefunctionTreatmentofBonding 50
3.3 Low-LyingStatesofSFandOF 53
3.4 Low-LyingStatesofSF andOF (andBeyond) 58
2 2
3.4.1 SF (X1A ) 58
2 1
3.4.2 SF (a3B ) 59
2 1
3.4.3 SF (b3A ) 61
2 2
3.4.4 OF (X1A ) 62
2 1
3.4.5 TripletstatesofOF 62
2
3.4.6 SF andSF 63
3 4
3.4.7 SF andSF 64
5 6
3.5 ComparisontoOtherModels 64
3.5.1 Rundle–Pimentel3c-4eModel 64
3.5.2 DiabaticStatesModel 66
3.5.3 DemocracyPrinciple 67
3.6 ConcludingRemarks 67
References 68
4 Donor–AcceptorComplexesofMain-GroupElements 71
GernotFrenkingandRalfTonner
4.1 Introduction 71
4.2 Single-CenterComplexesEL 73
2
4.2.1 CarbonesCL 73
2
4.2.2 IsoelectronicGroup15andGroup13Homologues(N+)L and
2
(BH)L 82
2
4.2.3 Donor–AcceptorBondinginHeavierTetrylenesER andTetrylones
2
EL (E=Si–Pb) 88
2
4.3 Two-CenterComplexesE L 94
2 2
4.3.1 Two-CenterGroup14ComplexesSi L –Pb L (L=NHC) 95
2 2 2 2
4.3.2 Two-CenterGroup13andGroup15ComplexesB L andN L 101
2 2 2 2
4.4 SummaryandConclusion 110
References 110
Contents VII
5 Electron-CountingRulesinClusterBonding–PolyhedralBoranes,
ElementalBoron,andBoron-RichSolids 113
ChakkingalP.PriyakumariandEluvathingalD.Jemmis
5.1 Introduction 113
5.2 Wade’sRule 114
5.3 LocalizedBondingSchemesforBondinginPolyhedralBoranes 119
5.4 4n+2InterstitialElectronRuleandRing-CapOrbitalOverlap
Compatibility 122
5.5 CappingPrinciple 125
5.6 ElectronicRequirementofCondensedPolyhedralBoranes–mno
Rule 126
5.7 FactorsAffectingtheStabilityofCondensedPolyhedralClusters 134
5.7.1 Exo-polyhedralInteractions 134
5.7.2 OrbitalCompatibility 135
5.8 HypoelectronicMetallaboranes 136
5.9 ElectronicStructureofElementalBoronandBoron-RichMetal
Borides–ApplicationofElectron-CountingRules 139
5.9.1 α-RhombohedralBoron 139
5.9.2 β-RhombohedralBoron 140
5.9.3 AlkaliMetal-IndiumClusters 142
5.9.4 ElectronicStructureofMg∼5B44 143
5.10 Conclusion 144
References 145
6 BoundTripletPairsintheHighestSpinStatesofMonovalentMetal
Clusters 149
DavidDanovichandSasonShaik
6.1 Introduction 149
6.2 CanTripletPairsBeBonded? 150
6.2.1 APrototypicalBoundTripletPairin3Li 150
2
6.2.2 TheNPFMBondedSeriesofn+1Li (n=2−10) 152
n
6.3 OriginsofNPFMBondinginn+1Li Clusters 152
n
6.3.1 OrbitalCartoonsfortheNPFMBondingofthe3Σ+StateofLi 154
u 2
6.4 GeneralizationofNPFMBondinginn+1Li Clusters 156
n
6.4.1 VBMixingDiagramRepresentationoftheBondingin3Li 156
2
6.4.2 VBModelingofn+1Li Patterns 158
n
6.5 NPFMBondinginCoinageMetalClusters 161
6.5.1 StructuresandBondingofCoinageMetalNPFMClusters 161
6.6 ValenceBondModelingoftheBondinginNPFMClustersofthe
CoinageMetals 163
6.7 NPFMBonding:ResonatingBoundTripletPairs 167
6.8 ConcludingRemarks:BoundTripletPairs 168
Appendix 170
6.A MethodsandSomeDetailsofCalculations 170
6.B SymmetryAssignmentoftheVBWaveFunction 170
VIII Contents
6.C TheVBConfigurationCountandtheExpressionsforDeforNPFM
Clusters 171
References 172
7 ChemicalBondinginTransitionMetalCompounds 175
GernotFrenking
7.1 Introduction 175
7.2 ValenceOrbitalsandHybridizationinElectron-SharingBondsof
TransitionMetals 177
7.3 CarbonylComplexesTM(CO) q(TMq =Hf2−,Ta−,W,Re+,Os2+,
6
Ir3+) 181
7.4 PhosphaneComplexes(CO) TM-PR andN-HeterocyclicCarbene
5 3
Complexes(CO) TM-NHC(TM=Cr,Mo,W) 187
5
7.5 EthyleneandAcetyleneComplexes(CO) TM-C H andCl TM-C H
5 2 n 4 2 n
(TM=Cr,Mo,W) 190
7.6 Group-13DiylComplexes(CO) Fe-ER(E=B–Tl;R=Ph,Cp) 195
4
7.7 FerroceneFe(η5-Cp) andBis(benzene)chromiumCr(η6-Bz) 199
2 2
7.8 Cluster,Complex,orElectron-SharingCompound?Chemical
BondinginMo(EH) andPd(EH) (E=Zn,Cd,Hg) 203
12 8
7.9 Metal–MetalMultipleBonding 211
7.10 Summary 214
Acknowledgment 214
References 214
8 ChemicalBondinginOpen-ShellTransition-MetalComplexes 219
KatharinaBoguslawskiandMarkusReiher
8.1 Introduction 219
8.2 TheoreticalFoundations 220
8.2.1 DefinitionofOpen-ShellElectronicStructures 221
8.2.2 TheConfigurationInteractionAnsatz 222
8.2.2.1 TheTruncationProcedure 222
8.2.2.2 DensityMatrices 222
8.2.3 AbInitioSingle-ReferenceApproaches 223
8.2.4 AbInitioMultireferenceApproaches 224
8.2.5 DensityFunctionalTheoryforOpen-ShellMolecules 229
8.3 QualitativeInterpretation 230
8.3.1 LocalSpin 230
8.3.2 BrokenSpinSymmetry 233
8.3.3 AnalysisofBondOrders 235
8.3.4 AtomsinMolecules 237
8.3.5 EntanglementMeasuresforSingle-andMultireferenceCorrelation
Effects 239
8.4 SpinDensityDistributions—ACaseStudy 243
8.4.1 AOne-DeterminantPicture 243
8.4.2 AMulticonfigurationalStudy 245