Organometallic Compounds: Synthesis, Reactions, and Applications

440 Pages·2023·7.02 MB·English

by  Verma D.K., Aslam J. (ed.)

OrganometallicCompounds
Organometallic Compounds
Synthesis, Reactions, and Applications
Edited by
Dakeshwar Kumar Verma
Jeenat Aslam
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v
Contents
Preface xix
AbouttheEditors xxi
1 OrganometallicCompounds:TheFundamentalAspects 1
GeethaB.MarkandeyaandSrinivasaBudagumpi
1.1 Introduction 1
1.1.1 OrganometallicChemistry 1
1.1.2 OrganometallicCompounds 1
1.1.3 StructureofOrganometallicCompound 1
1.2 MilestonesinOrganometallicCompounds 2
1.2.1 Equation(1.1):SynthesisofFirstOrganometallicCompound 2
1.2.2 Equation(1.2):PreparationofZeise’sSalt 2
1.2.3 Equations(1.3)–(1.5):PreparationofOrganochlorosilaneCompound 3
1.2.4 Equation(1.6):SynthesisofFirstMetalCarbonylCompound 3
1.2.5 Equation(1.7):SynthesisofFirstBinaryMetalCarbonylComplex 3
1.2.6 Equation(1.8):BarbierReaction 3
1.2.7 Equation(1.9):SynthesisofOrganicCompoundUsingaGrignard
Reagent 4
1.2.8 Equations(1.10)and(1.11):SynthesisofAlkyllithiumCompound 4
1.2.9 Equations(1.12)and(1.13):SynthesisofOrganolithiumCompound 4
1.2.10 Equation(1.14):HydroformylationReaction 4
1.2.11 Equation(1.15):SynthesisofOrganochlorosilaneCompound 4
1.2.12 Equation(1.16):TrimerizationofAcetylene 5
1.2.13 Equation(1.17):SynthesisofFerrocene 5
1.2.14 Equation(1.18):AsymmetricCatalysisReaction 5
1.2.15 Equation(1.19):PalladiumCatalyzedSuzukiCouplingReaction 6
1.2.16 Equation(1.20):SynthesisofBuckyFerrocene 8
1.3 StabilityofOrganometallicCompounds 9
1.4 PropertiesofOrganometallicCompounds 9
1.5 BasicConceptsinOrganometallicCompounds 9
1.5.1 18-ElectronRule 9
1.5.1.1 Statementof18ElectronRule 10
1.5.1.2 Examples 11
vi Contents
1.5.2 Π–BackBondingorBackDonation 12
1.5.3 Hapticityηx 12
1.6 HapticityofLigands 12
1.7 ChangeinHapticity 13
1.8 HapticityVersesDenticity 14
1.9 CountingofElectronsandFindingoutMetal–MetalBonds 15
1.9.1 CalculatingtheNumberofMetal–MetalBonds 15
1.9.2 WritingtheProbableStructureofCompound 15
1.9.3 HowtoDrawtheProbableStructureofNi(η1-C H )(η3-C H ) 15
3 5 3 5
1.9.4 HowtoDrawtheProbableStructureof(μ-CO)-[η5-CpRh] (CO) 15
3
1.10 MetalsofOrganometallicCompounds 16
1.10.1 OrganometallicCompoundsofTransitionMetals 17
1.10.2 TheBondingandStructureinDifferentMetalcomplexes 17
1.10.2.1 AlkeneComplexes 17
1.10.2.2 AllylComplexes 17
1.10.2.3 CarbonylComplexes 17
1.10.2.4 Metallocenes 18
1.10.2.5 DihydrogenComplexes 18
1.10.2.6 TransitionMetalCarbeneComplex 18
1.11 ImportanceofOrganometallicCompounds 19
1.11.1 TypesofOrganometallicCompounds 19
1.11.2 UsesofOrganometallicCompounds 20
1.12 Conclusions 20
References 21
2 NomenclatureofOrganometallicCompounds 25
RajK.Rathore,SadhucharanMallick,andBhavabhutiPrasad
2.1 Introduction 25
2.2 AimoftheNomenclature 26
2.3 TypeofNomenclatureSystem 26
2.3.1 BinaryNomenclature 26
2.3.2 SubstitutiveNomenclature 27
2.3.3 AdditiveNomenclatureorCoordinationnomenclature 27
2.4 ConceptsandConventions 28
2.4.1 OxidationNumber 28
2.4.2 CoordinationNumber 29
2.4.3 Chelation 29
2.4.4 Ligands 29
2.4.5 SpecifyingConnectivity–TheKappa(κ)Convention 30
2.4.6 BridgingLigands–TheMu(μ)Convention 31
2.4.7 Hapticity–TheEta(η)Convention 33
2.5 RegulationsConcerningtheNomenclatureofTransitionElement
OrganometallicCompounds 36
References 46
Contents vii
3 ClassificationofOrganometallicCompounds 47
MukeshK.Tyagi,GokulR.Nishad,DakeshwarKumarVerma,LeiGuo,and
ElyorBerdimurodov
3.1 Introduction 47
3.2 ClassificationofOrganometallicCompound 48
3.2.1 Sigma-BondedOrganometallicCompound 48
3.2.2 π-BondedOrganometallicCompounds 50
3.2.3 IonicBondedOrganometallicCompounds 51
3.2.4 MulticenteredBondedOrganometallicCompounds 53
3.2.4.1 BasedonHeptacity(η1toη8): 53
3.3 GrignardReagent(G.R.) 54
3.3.1 PhysicalProperties 54
3.3.2 ChemicalProperties 54
3.3.2.1 Alkanes 54
3.3.2.2 Alkenes 56
3.3.2.3 Alkynes 56
3.3.2.4 Ethers 56
3.3.2.5 Reactionwithcarbondioxide 56
3.3.2.6 InsertionReaction 56
3.3.2.7 SynthesisofSilicones 56
3.3.2.8 NucleophilicSubstitution 57
3.4 OrganozincCompounds 59
3.4.1 PhysicalProperties 59
3.4.2 ChemicalProperties 59
3.5 OrganolithiumCompounds 61
3.5.1 ReactionResemblingGrignardReagents 61
3.5.2 ReactionsDifferentfromGrignardReagents 64
3.6 OrganosulfurCompounds 65
3.6.1 PhysicalProperties 65
3.6.2 ChemicalProperties 65
3.6.3 PropertiesDifferentfromAlcohols 67
3.7 Conclusion 69
References 69
4 SynthesisMethodsofOrganometallicCompounds 71
OmarDagdag,RajeshHaldhar,Seong-CheolKim,ElyorBerdimurodov,
EkeminiD.Akpan,andEnoE.Ebenso
4.1 Introduction 71
4.2 SynthesisMethodsofOrganometallicCompounds 72
4.2.1 ElectrochemicalMethodsfortheSynthesisofOrganometallic
Compounds 72
4.2.1.1 SynthesisofCyanoCu(I)ComplexesintheElectrochemicalCell 72
4.2.1.2 SynthesisofanOrganorheniumCyclopentadienylComplexinthe
ElectrochemicalCell 72
viii Contents
4.2.1.3 SynthesisofN-heterocyclicCarbeneComplexesinthe
ElectrochemicalCell 73
4.2.1.4 SynthesisofOrganocopper(I)π-ComplexesintheElectrochemical
Cell 73
4.2.1.5 SynthesisofOrganonickelσ-ComplexesintheElectrochemicalCell 73
4.2.2 SynthesisofOrganicCompoundsintheElectrochemicalCellbyMetal
organicCatalysts 75
4.2.2.1 TheSynthesisofOrganicCompoundsintheElectrochemicalCell
bytheNi-OrganicCatalyze 75
4.2.2.2 TheSynthesisofOrganicCompoundsintheElectrochemicalCell
bythePd-OrganicCatalyses 75
4.2.2.3 SynthesisofOrganicCompoundsintheElectrochemicalCellbythe
Sm-OrganicCatalyses 78
4.2.3 SynthesisofOrganometallicNucleosides 79
4.2.3.1 ACategory:MainCompounds 79
4.2.3.2 A1Subcategory:MainCompounds 79
4.2.3.3 BCategory:MainCompounds 80
4.2.3.4 CCategory:MainCompounds 81
4.2.3.5 C1Subcategory:MainCompounds 81
4.2.3.6 DCategories:MainCompounds 82
4.3 Conclusions 84
Acknowledgment 84
AuthorsContributions 84
ConflictsofInterest 84
References 84
5 MetalCarbonyls:Synthesis,Properties,andStructure 87
RameshRengan
5.1 Introduction 87
5.2 ClassificationofMetalCarbonyls 87
5.2.1 ClassificationBasedonCoordinatedLigands 87
5.2.1.1 HomolepticCarbonyls 88
5.2.1.2 HeterolepticCarbonyls 88
5.2.2 ClassificationBasedonNumberofMetalsandtheConstitutionof
Carbonyls 88
5.2.2.1 MononuclearCarbonylComplexes 88
5.2.2.2 PolynuclearCarbonylComplexes 89
5.3 SynthesisofMetalCarbonyls 90
5.3.1 DirectReactionofMetalwithCarbonMonoxide 90
5.3.2 ReductiveCarbonylation 90
5.3.3 PhotolysisandThermolysis 91
5.3.4 AbstractionofCOfromaReactiveOrganicCarbonylCompounds 91
5.4 PropertiesofMetalCarbonyls 92
5.4.1 PhysicalProperties 92
5.4.2 ChemicalProperties 92
Contents ix
5.4.2.1 LigandSubstitutionReactions 92
5.4.2.2 ReactionwithSodiumMetal 95
5.4.2.3 ReactionwithSodiumHydroxide 95
5.4.2.4 ReactionwithHalogens 95
5.4.2.5 ReactionwithHydrogen 96
5.4.2.6 ReactionwithNitricoxide(NO) 96
5.4.2.7 Disproportionation 96
5.5 StructureofMetalCarbonyls 97
5.5.1 StructuresofSomeMononuclearCarbonylComplexes 97
5.5.2 StructuresofSomeBiandPolynuclearCarbonylComplexes 98
5.6 BondinginMetalCarbonyls 99
5.6.1 FormationofMixedAtomicOrbitals 99
5.7 SynergisticEffect 103
5.8 Conclusion 103
FurtherReading 104
References 104
6 Metal–CarbonMultipleBondedCompounds 107
RakeshKumarSahu,MukeshKumarTyagi,andRajeshHaldhar
6.1 Introduction 107
6.2 Nomenclature 109
6.3 Classifications 111
6.3.1 Metal–alkylideneComplexes 111
6.3.2 Metal–alkylidyneComplexes 111
6.4 Structure 111
6.4.1 Alkylidene(Carbene) 111
6.4.2 Carbyne(Alkylidyne) 113
6.5 PreparationMethods 114
6.5.1 Metal–alkylideneComplexes 114
6.5.1.1 ByNucleophilicCarbene 115
6.5.1.2 ByElectrophilicAlkylidenes 116
6.5.2 Metal–alkylidyneComplexes 118
6.6 ImportantReactions 119
6.6.1 ReactionofAlkylideneMetathesis 119
6.6.2 ImportantReactionofAlkylidyneMetathesis 124
6.7 Applications 125
References 127
7 Metallocene:Synthesis,Properties,andStructure 131
AmarpreetK.Bhatia,PriyankaSingh,andShippiDewangan
7.1 Introduction 131
7.2 StructureofMetallocene 132
7.3 SynthesisofMetallocene 134
7.4 ChemicalPropertiesofMetallocene 136
7.4.1 FerroceneandItsDerivatives 136
x Contents
7.4.2 OtherMetalloceneSandwiches 138
7.4.3 Main-groupMetallocene 139
7.4.4 Metal–bis-areneSandwichComplexes 140
7.4.4.1 GeneralView 140
7.4.4.2 Structure 142
7.4.4.3 Reactions 142
7.5 Conclusion 144
References 144
8 𝛔-Complexes,𝛑-Complexes,and𝛈n-C R Carbocyclic
n n
Polyenes-BasedOrganometallicCompounds 147
ShippiDewangan,JeenatAslam,andAmarpreetK.Bhatia
8.1 Introduction 147
8.2 σ-BondContainingOrganometallicCompounds 148
8.2.1 MetalCarbonyl 148
8.2.1.1 GeneralOverview 148
8.2.1.2 SynthesesofMetalCarbonyls 148
8.2.1.3 StructureofMetalCarbonyls 149
8.2.1.4 ReactionsofMetalCarbonyls 150
8.2.2 Metal–Alkyl,–Vinyl,and–HydrideComplexes 150
8.2.2.1 MetalAlkyls 150
8.2.2.2 MetalVinyls 152
8.2.2.3 MetalHydrides 152
8.2.2.4 Metal–CarbeneComplexes 154
8.3 π-BondContainingOrganometallicCompounds 156
8.3.1 Metal–OlefinComplexes 156
8.3.1.1 GeneralOverview 156
8.3.1.2 SynthesesofMetal–OlefinComplexes 157
8.3.1.3 ReactionsofMetal–OlefinComplexes 157
8.3.2 Metal–DieneComplexes 157
8.3.3 Metal–AlkyneComplexes 158
8.3.4 π–AllylComplexes 158
8.3.4.1 Structureofπ–AllylComplexes 158
8.3.4.2 Synthesesofπ–AllylComplexes 159
8.3.4.3 Reactionsofπ–AllylComplexes 160
8.4 ηn-C R CarbocyclicPolyenesContainingOrganometallic
n n
Compounds 161
8.4.1 Cyclopropenyls,η3-C R 161
3 3
8.4.2 Cyclobutadienes,η4-C R 161
4 4
8.4.3 Cyclopentadienyls,η5-C R 162
5 5
8.4.3.1 GeneralOverview 162
8.4.3.2 StructureofMetallocene 162
8.4.3.3 SynthesesofMetallocene 163
8.4.3.4 ChemicalPropertiesofMetallocene 164
8.4.3.5 ApplicationsofMetallocene 165