Organometallic Compounds: Synthesis, Reactions, and Applications

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Title Page
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Contents
Preface
About the Editors
Chapter 1 Organometallic Compounds: The Fundamental Aspects
1.1 Introduction
1.1.1 Organometallic Chemistry
1.1.2 Organometallic Compounds
1.1.3 Structure of Organometallic Compound
1.2 Milestones in Organometallic Compounds
1.2.1 Equation (1.1): Synthesis of First Organometallic Compound
1.2.2 Equation (1.2): Preparation of Zeise's Salt
1.2.3 Equations (1.3)–(1.5): Preparation of Organochlorosilane Compound
1.2.4 Equation (1.6): Synthesis of First Metal Carbonyl Compound
1.2.5 Equation (1.7): Synthesis of First Binary Metal Carbonyl Complex
1.2.6 Equation (1.8): Barbier Reaction
1.2.7 Equation (1.9): Synthesis of Organic Compound Using a Grignard Reagent
1.2.8 Equations (1.10) and (1.11): Synthesis of Alkyllithium Compound
1.2.9 Equations (1.12) and (1.13): Synthesis of Organolithium Compound
1.2.10 Equation (1.14): Hydroformylation Reaction
1.2.11 Equation (1.15): Synthesis of Organochlorosilane Compound
1.2.12 Equation (1.16): Trimerization of Acetylene
1.2.13 Equation (1.17): Synthesis of Ferrocene
1.2.14 Equation (1.18): Asymmetric Catalysis Reaction
1.2.15 Equation (1.19): Palladium Catalyzed Suzuki Coupling Reaction
1.2.16 Equation (1.20): Synthesis of Bucky Ferrocene
1.3 Stability of Organometallic Compounds
1.4 Properties of Organometallic Compounds
1.5 Basic Concepts in Organometallic Compounds
1.5.1 18‐Electron Rule
1.5.1.1 Statement of 18 Electron Rule
1.5.1.2 Examples
1.5.2 Π –Back Bonding or Back Donation
1.5.3 Hapticity ηx
1.6 Hapticity of Ligands
1.7 Change in Hapticity
1.8 Hapticity Verses Denticity
1.9 Counting of Electrons and Finding out Metal–Metal Bonds
1.9.1 Calculating the Number of Metal–Metal Bonds
1.9.2 Writing the Probable Structure of Compound
1.9.3 How to Draw the Probable Structure of Ni(η1‐C3H5) (η3‐C3H5)
1.9.4 How to Draw the Probable Structure of (μ‐CO)‐[η5‐CpRh]3(CO)
1.10 Metals of Organometallic Compounds
1.10.1 Organometallic Compounds of Transition Metals
1.10.2 The Bonding and Structure in Different Metal complexes
1.10.2.1 Alkene Complexes
1.10.2.2 Allyl Complexes
1.10.2.3 Carbonyl Complexes
1.10.2.4 Metallocenes
1.10.2.5 Dihydrogen Complexes
1.10.2.6 Transition Metal Carbene Complex
1.11 Importance of Organometallic Compounds
1.11.1 Types of Organometallic Compounds
1.11.2 Uses of Organometallic Compounds
1.12 Conclusions
References
Chapter 2 Nomenclature of Organometallic Compounds
2.1 Introduction
2.2 Aim of the Nomenclature
2.3 Type of Nomenclature System
2.3.1 Binary Nomenclature
2.3.2 Substitutive Nomenclature
2.3.3 Additive Nomenclature or Coordination nomenclature
2.4 Concepts and Conventions
2.4.1 Oxidation Number
2.4.2 Coordination Number
2.4.3 Chelation
2.4.4 Ligands
2.4.5 Specifying Connectivity – The Kappa (κ) Convention
2.4.6 Bridging Ligands – The Mu (μ) Convention
2.4.7 Hapticity – The Eta (η) Convention
2.5 Regulations Concerning the Nomenclature of Transition Element Organometallic Compounds
References
Chapter 3 Classification of Organometallic Compounds
3.1 Introduction
3.2 Classification of Organometallic Compound
3.2.1 Sigma‐Bonded Organometallic Compound
3.2.2 π‐Bonded Organometallic Compounds
3.2.3 Ionic Bonded Organometallic Compounds
3.2.4 Multicentered Bonded Organometallic Compounds
3.2.4.1 Based on Heptacity (η1 to η8):
3.3 Grignard Reagent (G.R.)
3.3.1 Physical Properties
3.3.2 Chemical Properties
3.3.2.1 Alkanes
3.3.2.2 Alkenes
3.3.2.3 Alkynes
3.3.2.4 Ethers
3.3.2.5 Reaction with carbon dioxide
3.3.2.6 Insertion Reaction
3.3.2.7 Synthesis of Silicones
3.3.2.8 Nucleophilic Substitution
3.4 Organozinc Compounds
3.4.1 Physical Properties
3.4.2 Chemical Properties
3.5 Organolithium Compounds
3.5.1 Reaction Resembling Grignard Reagents
3.5.2 Reactions Different from Grignard Reagents
3.6 Organosulfur Compounds
3.6.1 Physical Properties
3.6.2 Chemical Properties
3.6.3 Properties Different from Alcohols
3.7 Conclusion
References
Chapter 4 Synthesis Methods of Organometallic Compounds
4.1 Introduction
4.2 Synthesis Methods of Organometallic Compounds
4.2.1 Electrochemical Methods for the Synthesis of Organometallic Compounds
4.2.1.1 Synthesis of Cyano Cu(I) Complexes in the Electrochemical Cell
4.2.1.2 Synthesis of an Organorhenium Cyclopentadienyl Complex in the Electrochemical Cell
4.2.1.3 Synthesis of N‐heterocyclic Carbene Complexes in the Electrochemical Cell
4.2.1.4 Synthesis of Organocopper (I) π‐Complexes in the Electrochemical Cell
4.2.1.5 Synthesis of Organonickel σ‐Complexes in the Electrochemical Cell
4.2.2 Synthesis of Organic Compounds in the Electrochemical Cell by Metal organic Catalysts
4.2.2.1 The Synthesis of Organic Compounds in the Electrochemical Cell by the Ni‐Organic Catalyze
4.2.2.2 The Synthesis of Organic Compounds in the Electrochemical Cell by the Pd‐Organic Catalyses
4.2.2.3 Synthesis of Organic Compounds in the Electrochemical Cell by the Sm‐Organic Catalyses
4.2.3 Synthesis of Organometallic Nucleosides
4.2.3.1 A Category: Main Compounds
4.2.3.2 A1 Subcategory: Main Compounds
4.2.3.3 B Category: Main Compounds
4.2.3.4 C Category: Main Compounds
4.2.3.5 C1 Subcategory: Main Compounds
4.2.3.6 D Categories: Main Compounds
4.3 Conclusions
Acknowledgment
Authors Contributions
Conflicts of Interest
References
Chapter 5 Metal Carbonyls: Synthesis, Properties, and Structure
5.1 Introduction
5.2 Classification of Metal Carbonyls
5.2.1 Classification Based on Coordinated Ligands
5.2.1.1 Homoleptic Carbonyls
5.2.1.2 Heteroleptic Carbonyls
5.2.2 Classification Based on Number of Metals and the Constitution of Carbonyls
5.2.2.1 Mononuclear Carbonyl Complexes
5.2.2.2 Polynuclear Carbonyl Complexes
5.3 Synthesis of Metal Carbonyls
5.3.1 Direct Reaction of Metal with Carbon Monoxide
5.3.2 Reductive Carbonylation
5.3.3 Photolysis and Thermolysis
5.3.4 Abstraction of CO from a Reactive Organic Carbonyl Compounds
5.4 Properties of Metal Carbonyls
5.4.1 Physical Properties
5.4.2 Chemical Properties
5.4.2.1 Ligand Substitution Reactions
5.4.2.2 Reaction with Sodium Metal
5.4.2.3 Reaction with Sodium Hydroxide
5.4.2.4 Reaction with Halogens
5.4.2.5 Reaction with Hydrogen
5.4.2.6 Reaction with Nitricoxide (NO)
5.4.2.7 Disproportionation
5.5 Structure of Metal Carbonyls
5.5.1 Structures of Some Mononuclear Carbonyl Complexes
5.5.2 Structures of Some Bi and Polynuclear Carbonyl Complexes
5.6 Bonding in Metal Carbonyls
5.6.1 Formation of Mixed Atomic Orbitals
5.7 Synergistic Effect
5.8 Conclusion
Further Reading
References
Chapter 6 Metal–Carbon Multiple Bonded Compounds
6.1 Introduction
6.2 Nomenclature
6.3 Classifications
6.3.1 Metal–alkylidene Complexes
6.3.2 Metal–alkylidyne Complexes
6.4 Structure
6.4.1 Alkylidene (Carbene)
6.4.2 Carbyne (Alkylidyne)
6.5 Preparation Methods
6.5.1 Metal–alkylidene Complexes
6.5.1.1 By Nucleophilic Carbene
6.5.1.2 By Electrophilic Alkylidenes
6.5.2 Metal–alkylidyne Complexes
6.6 Important Reactions
6.6.1 Reaction of Alkylidene Metathesis
6.6.2 Important Reaction of Alkylidyne Metathesis
6.7 Applications
References
Chapter 7 Metallocene: Synthesis, Properties, and Structure
7.1 Introduction
7.2 Structure of Metallocene
7.3 Synthesis of Metallocene
7.4 Chemical Properties of Metallocene
7.4.1 Ferrocene and Its Derivatives
7.4.2 Other Metallocene Sandwiches
7.4.3 Main‐group Metallocene
7.4.4 Metal–bis‐arene Sandwich Complexes
7.4.4.1 General View
7.4.4.2 Structure
7.4.4.3 Reactions
7.5 Conclusion
References
Chapter 8 σ‐Complexes, π‐Complexes, and ηn‐CnRn Carbocyclic Polyenes‐Based Organometallic Compounds
8.1 Introduction
8.2 σ‐Bond Containing Organometallic Compounds
8.2.1 Metal Carbonyl
8.2.1.1 General Overview
8.2.1.2 Syntheses of Metal Carbonyls
8.2.1.3 Structure of Metal Carbonyls
8.2.1.4 Reactions of Metal Carbonyls
8.2.2 Metal–Alkyl, –Vinyl, and –Hydride Complexes
8.2.2.1 Metal Alkyls
8.2.2.2 Metal Vinyls
8.2.2.3 Metal Hydrides
8.2.2.4 Metal–Carbene Complexes
8.3 π‐Bond Containing Organometallic Compounds
8.3.1 Metal–Olefin Complexes
8.3.1.1 General Overview
8.3.1.2 Syntheses of Metal–Olefin Complexes
8.3.1.3 Reactions of Metal–Olefin Complexes
8.3.2 Metal–Diene Complexes
8.3.3 Metal–Alkyne Complexes
8.3.4 π–Allyl Complexes
8.3.4.1 Structure of π–Allyl Complexes
8.3.4.2 Syntheses of π–Allyl Complexes
8.3.4.3 Reactions of π–Allyl Complexes
8.4 ηn‐CnRn Carbocyclic Polyenes Containing Organometallic Compounds
8.4.1 Cyclopropenyls, η3‐C3R3
8.4.2 Cyclobutadienes, η4‐C4R4
8.4.3 Cyclopentadienyls, η5‐C5R5
8.4.3.1 General Overview
8.4.3.2 Structure of Metallocene
8.4.3.3 Syntheses of Metallocene
8.4.3.4 Chemical Properties of Metallocene
8.4.3.5 Applications of Metallocene
8.5 Conclusion
References
Chapter 9 Organometallic Complexes of the Lanthanides and Actinides
9.1 Introduction
9.2 Methods of Preparation
9.2.1 Salt Elimination
9.2.2 Metal Vapor Synthesis Method
9.2.3 Metathesis Reaction Method
9.2.4 σ‐Bond Metathesis
9.2.5 Acid–Base Method
9.3 Organometallic Compounds of Lanthanides
9.3.1 Types
9.3.1.1 σ‐Bonded Complexes
9.3.1.2 π‐Bonded Organometallic Compounds
9.4 Organometallic Compounds of Actinides
9.4.1 Types
9.4.2 σ‐Bonded Complexes
9.4.3 π‐Bonded Complexes
9.4.3.1 Cyclopentadienyl Derivatives
9.5 Stability
9.5.1 Maintaining Anhydrous and Anaerobic Conditions
9.5.2 Avoiding Elimination Reactions
9.5.3 Blocking the Coordination Sites
9.5.4 Donor‐functionalized Chelating Pendant Donor Ligands
9.6 Properties
9.6.1 Thermodynamic and Kinetic Considerations
9.6.2 Solvation
9.6.3 Aggregation
9.6.4 Donor–Acceptor Interactions
9.6.5 Salt Occlusion or Ate Complexation
9.6.6 Neutral π‐Donor Ligation
9.6.7 Agostic Interactions
9.6.8 Complex Agglomeration
9.6.9 Ligand Exchange and Redistribution Reactions
9.6.10 Insertion Reactions
9.6.11 Elimination Reactions
9.6.12 Redox Chemistry
9.6.13 Reaction Sequences – Catalytic Cycles
9.7 Applications of Organolanthanoids and Organoactinoids
9.7.1 Catalytic Applications
9.7.1.1 Catalysis of Polymerization
9.7.1.2 Catalysts and Reagents for Reduction Processes
9.7.1.3 Catalysts and Reagents for Oxidation Processes
9.7.2 Miscellaneous Applications
9.8 Conclusion
Further Reading
Chapter 10 Bioorganometallic Chemistry
10.1 Introduction
10.2 Cobalamin: Vitamin B12‐Coenzyme
10.2.1 Occurrence and Function
10.2.2 Structure
10.2.3 B12‐dependent Enzymes
10.2.4 Occurrence
10.2.5 Function
10.3 Metalloproteins
10.3.1 Occurrence
10.3.2 Functions
10.3.3 Electron Transferases
10.3.3.1 Flavodoxins
10.3.3.2 Blue Copper Proteins
10.3.3.3 Iron–Sulfur Proteins
10.3.3.4 Cytochromes
10.4 Oxidoreductase
10.4.1 Iron–Porphyrin Complexes
10.4.2 Monooxygenases
10.5 Nitrogenases‐catalyzing Nitrogen Fixation
10.6 Nickel Enzymes: CODH
10.7 Conclusion
References
Chapter 11 Important Reactions of Organometallic Compounds
11.1 Introduction
11.2 Reactions Involving Gain or Loss of Ligands
11.2.1 Associative and Dissociative Substitution
11.2.1.1 Dissociation of Carbonyls
11.2.1.2 Dissociation of Nitrosyls
11.2.1.3 Dissociation of Phosphine
11.2.2 Oxidative Addition and CH Bond Activation
11.2.2.1 Mechanism
11.2.2.2 Binuclear Oxidative Addition
11.2.2.3 Cyclometallations
11.2.2.4 Nucleophilic Displacement
11.3 Reductive Elimination and Pd‐catalyzed Cross Coupling
11.4 Reactions Involving Modification of Ligands
11.4.1 Insertion
11.4.1.1 Carbonyl Insertion (Alkyl Migration)
11.4.1.2 Olefin Insertion
11.4.1.3 Other Insertion Reaction
11.4.2 Hydride Elimination
11.4.2.1 Avoidance of β‐hydrogen Elimination
11.4.3 Abstraction
11.4.3.1 Nucleophilic Abstraction
11.5 Conclusion
References
Chapter 12 Characterization Techniques of Organometallic Compounds
12.1 Introduction
12.2 Conventional Methods
12.2.1 Nuclear Magnetic Resonance (NMR) Spectroscopy
12.2.2 Infrared and Raman Spectroscopy
12.2.3 UV–Visible Spectroscopy
12.2.4 X‐Ray Crystallography
12.2.5 Mass Spectroscopy
12.2.6 Elemental Analysis
12.3 Unconventional Methods
12.3.1 Neutron Activation Analysis
12.3.2 X‐Ray Photoelectron Spectroscopy
12.3.3 Electron Diffraction Crystallography and Microelectron Diffraction
12.3.4 Mössbauer Spectroscopy
12.3.5 Electroanalytical Methods
12.4 Conclusion
References
Chapter 13 Organometallic Reagents
13.1 Organoboron Reagents
13.1.1 Introduction
13.1.2 Main Organoboron Reagents and Their Reactions
13.1.2.1 Hydroboration and Subsequent Reactions
13.1.2.2 Suzuki Coupling
13.1.2.3 Acyltrifluoroborates
13.1.2.4 Allylation
13.1.2.5 Chan–Lam coupling
13.1.2.6 Petasis Reaction
13.2 Organocopper Reagents
13.2.1 Introduction
13.2.2 Types of Organocuprates Reagents
13.2.2.1 Gilman Reagent (R2CuM)
13.2.2.2 Higher Order Organocuprates (R2CuCNLi2)
13.2.2.3 Grignard Copper(I) Reagents (RMgX·CuY)
13.2.3 Reactions of Organocuprates
13.2.3.1 Increasing Chain Length of Alkyl halides
13.2.3.2 Alkylation of the Allylic Halides
13.2.3.3 Reaction with Vinyl Halides
13.2.3.4 Alkylation of Acyl Halides
13.2.3.5 Epoxide Opening
13.2.3.6 Conjugate Additions
13.2.3.7 Conjugate Addition in Presence of Lewis Acid and Electrophiles
13.2.3.8 O‐Trapping and C‐Trapping Reaction
13.2.3.9 Synthesis of Allenes
13.3 Organopalladium Reagents
13.3.1 Introduction
13.3.2 Types of C–C Cross‐Coupling Reaction Catalyzed by Palladium Metal
13.3.2.1 Heck Reaction
13.3.2.2 Negishi Coupling
13.3.2.3 Suzuki Coupling
13.3.2.4 Stille Coupling
13.3.2.5 Kumada Coupling
13.3.2.6 Hiyama Coupling
13.3.2.7 Sonogashira Coupling
13.3.2.8 Butchwald–Hartwig Coupling
13.3.2.9 Cyanation Reaction
13.3.2.10 Carbonylation Reaction
13.4 Grignard Reagents
13.4.1 Introduction
13.4.2 Synthesis
13.4.3 Reactivity
References
Chapter 14 Homogeneous and Heterogeneous Catalysis by Organometallic Complexes
14.1 Introduction
14.2 Organometallic Compounds and Homogeneous Catalysis
14.3 Catalytic Elementary Reactions
14.3.1 Isomerization
14.3.2 Alkene Isomerization
14.3.3 Alkyne Isomerization
14.3.4 Diene Isomerization
14.4 Hydrogenation
14.5 Carbon–Carbon Bond Formation
14.6 Metathesis
14.7 Oxidation
14.8 Reactions with Carbon Monoxide
14.9 Heterogenous Catalysis
14.9.1 Ziegler–Natta Catalyst
14.9.1.1 Stereoregularity
14.9.2 Water Gas Reaction
14.9.3 Zeolites
14.10 Conclusion
References
Chapter 15 Cluster Compounds: Boranes, Heteroboranes, and Metallaboranes
15.1 Introduction
15.1.1 Fundamentals of Cluster Compounds: Boranes, Heteroboranes, and Metallaboranes
15.2 Main Part
15.2.1 Cluster Compounds of Boranes and Heteroboranes: Synthesis, Reactions, and Applications
15.2.1.1 Basics
15.2.1.2 Synthesis
15.2.1.3 Reactions
15.2.1.4 Applications
15.2.2 Cluster Compounds of Metallaboranes: Synthesis, Reactions, and Applications
15.2.2.1 Basics
15.2.2.2 Synthesis
15.2.2.3 Reactions
15.2.2.4 Applications
15.3 Conclusion
References
Chapter 16 Applications of Organometallic Compounds for Carbon Dioxide Fixation, Reduction, Gas Adsorption, and Gas Purification
16.1 Organometallic Compounds for Fixation of CO2
16.2 Organometallic Compounds in Reduction of CO2
16.2.1 Nickel Complexes
16.2.2 Iron and Manganese Complexes
16.2.3 Copper and Cobalt Complexes
16.2.4 Palladium Complexes
16.2.5 Ruthenium, Rhenium, and Rhodium Complexes
16.2.6 N‐Heterocyclic Carbenes
16.3 Organometallic Compounds in Gas Adsorption and Purification
16.3.1 Metal Organic Frameworks (MOFs) for Gas Adsorption
16.3.2 Classification of MOFs as Adsorbents for Gas Separation
16.3.2.1 Rigid MOFs as Adsorbents for Selective Gas Separation
16.3.2.2 Flexible MOFs as Adsorbents for Gas Separation
16.4 Gas Purification with MOFs
16.4.1 Kinetic Separation
16.4.2 Quantum Sieving Effect for H2/D2 Separation
16.4.3 Membrane‐Based Gas Separation
References
Chapter 17 Emerging Role of Organometallic Compounds for Drug Delivery, Renewable Energy, and Wastewater Treatment
17.1 Introduction
17.2 Organometallic Compounds
17.3 Organometallic Compounds for Drug Delivery
17.4 Organometallic Compounds for Renewable Energy
17.5 Organometallic Compounds for Wastewater Treatment
17.6 Conclusion
17.7 Outlook
Acknowledgment
References
Chapter 18 Computational Approaches in Some Important Organometallic Catalysis Reaction
18.1 Introduction
18.2 Computational Method
18.2.1 Geometry Calculation
18.2.2 Energy
18.3 Organometallic Catalysis Reactions
18.3.1 Palladium
18.3.1.1 CH Bond Activation
18.3.1.2 Coupling Reactions
18.3.2 Nickel
18.3.2.1 Coupling Reactions
18.3.2.2 CO Bond Activation
18.3.2.3 Cyclization Reactions
18.3.2.4 Olefin Functionalization
18.3.3 Rhodium
18.3.3.1 Hydrogenation
18.3.3.2 Olefin Functionalization
18.3.3.3 Reactions of Rh Carbenoids and Nitrenoids
18.3.4 Iridium
18.3.4.1 Hydrogenation
18.3.4.2 Other Bond Activations
18.4 Conclusion
References
Index
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