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EditedbyGernotFrenkingand SasonShaik TheChemicalBond RelatedTitles Frenking,G.,Shaik,S.(eds.) Fleming,I. TheChemicalBond MolecularOrbitalsandOrganic FundamentalAspectsofChemical ChemicalReactions – Student Bonding Edition 2014 ISBN:978-3-527-33314-1; 2009 PrintISBN:978-0-470-74659-2; alsoavailableindigitalformats alsoavailableindigitalformats Reiher,M.,Wolf,A. Matta,C.F.,Boyd,R.J.(eds.) Relativistic QuantumChemistry TheQuantumTheoryofAtoms TheFundamentalTheoryofMolecular inMolecules Science SecondEdition FromSolidStatetoDNAandDrugDesign 2014 2007 PrintISBN:978-3-527-33415-5; PrintISBN:978-3-527-30748-7; alsoavailableindigitalformats alsoavailableindigitalformats Edited by Gernot Frenking and Sason Shaik The Chemical Bond Chemical Bonding Across the Periodic Table Editors AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, editors,andpublisherdonotwarrantthe Prof.Dr.GernotFrenking informationcontainedinthesebooks, Philipps-Universita¨tMarburg includingthisbook,tobefreeoferrors. FBChemie Readersareadvisedtokeepinmindthat Hans-Meerwein-Strasse statements,data,illustrations,procedural 35032Marburg detailsorotheritemsmayinadvertentlybe Germany inaccurate. Prof.Dr.SasonShaik LibraryofCongressCardNo.:appliedfor HebrewUniversity InstitutofChemistry GivatRamCampus BritishLibraryCataloguing-in-Publication 91904Jerusalem Data Israel Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Bibliographicinformationpublishedbythe DeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailedbibliographic dataareavailableontheInternetat <http://dnb.d-nb.de>. (cid:2)c 2014Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form–byphotoprinting,microfilm,orany othermeans–nortransmittedortranslated intoamachinelanguagewithoutwritten permissionfromthepublishers.Registered names,trademarks,etc.usedinthisbook, evenwhennotspecificallymarkedassuch, arenottobeconsideredunprotectedbylaw. PrintISBN:978-3-527-33315-8 ePDFISBN:978-3-527-66468-9 ePubISBN:978-3-527-66467-2 mobiISBN:978-3-527-66466-5 oBookISBN:978-3-527-66465-8 Cover-Design Adam-Design,Weinheim Typesetting LaserwordsPrivateLimited, Chennai,India PrintingandBinding betz-druckGmbH, Darmstadt Printedonacid-freepaper 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