Organometallic Mechanisms and Catalysis

Organometallic Mechanisms and Catalysis: The Role of Reactive Intermediates in Organic Processes covers the mechanistic delineation of organometallic chemistry and catalysis.
This book is organized into three parts encompassing 18 chapters. The first part describes first the oxidation-reduction process of organometals, followed by discussions on the catalytic reactions of peroxides, metal-catalyzed addition to olefins, and reduction of organic halides. This part also explores other reactions involving transition metal carbonyls and metal-catalyzed reactions of aromatic diazonium salts. The second part deals with some chemical aspects of organometals, such as their stability, thermochemistry, decomposition, hemolytic pathways, and the formation of carbon-carbon bonds. The third part examines the charge transfer processes and interactions of organometals with electron acceptors. This part further looks into the cleavage and insertion reactions of organometals with electrophiles, as well as the electrophilic and electron transfer mechanisms of organometals.
Organic and inorganic chemists, teachers, and students will greatly benefit from this book.

Inhalt

Preface

Glossary

Abbreviations

Chapter 1 Metal Catalysis in Organic Chemistry

References

Additional Reading

Part One Oxidation-Reduction Processes

Chapter 2 Homolytic Processes in Organic Oxidation-Reduction with Metal Complexes

I. Oxidation-Reduction between Inorganic Complexes

II. Oxidation-Reduction of Organic Compounds by Metal Complexes

III. Redox Chain Reactions in Metal-Catalyzed Processes

References

Additional Reading

Chapter 3 Organometal Free Radicals

I. Structural Types

II. Metal-Centered Radicals

III. Multicentered Radicals

IV. Carbon-Centered Organometal Radicals

V. Free Radical-Metal Complexes

References

Additional Reading

Chapter 4 Catalytic Reactions of Peroxides

I. Homolytic Mechanisms in Metal Catalysis

II. Heterolytic Mechanisms in Metal Catalysis

References

Additional Reading

Chapter 5 Metal Complexes in Organic Oxidations

I. Direct Oxidation

II. Catalytic Oxidations

References

Additional Reading

Chapter 6 Metal-Catalyzed Addition to Olefins

References

Additional Reading

Chapter 7 Reduction of Organic Halides

I. Chromium(II) and Cobalt(H) Reduction by Halogen Atom Transfer

II. Electron Transfer Reduction of Organic Halides

III. Radical Chain Processes in the Reduction of Alkyl Halides

IV. Reductions by Transition Metal Complexes: Oxidative Addition

References

Additional Reading

Chapter 8 Transition Metal Carbonyls

I. Ligand Substitution

II. Activation of Molecular Hydrogen

III. Hydrogen Transfer in Hydrido Carbonyl Metals

IV. Dissociation of Binuclear Carbonyl Metals

V. Oxidation of Carbonyl Metals

VI. Additions to Olefins

VII. Carbonylmetallate Anions

References

Additional Reading

Chapter 9 Metal-Catalyzed Reactions of Aromatic Diazonium Salts and Diazo Compounds

I. Aromatic Diazonium Salts

II. Diazo Compounds

References

Additional Reading

Part Two Chemistry of Organometals

Chapter 10 Stability of Organometals

I. Stable Alkylmetals

II. Thermal Decompositions of Organometals

III. Mechanistic Classifications for Thermolysis of Alkylmetals

IV. Alkylmetals as Intermediates in Catalytic Reactions

References

Additional Reading

Chapter 11 Thermochemistry of Organometals

References

Additional Reading

Chapter 12 Concerted Two-Equivalent Processes for the Decomposition of Alkylmetals

I. ß-Elimination of Alkyl Ligands

II. Reductive Coupling of Alkyl Ligands

III. Reductive Disproportionation and Coupling as Competing Pathways

IV. a-Elimination of Alkylmetals

V. Hydrogen and Alkyl Transfers to Alkylmetals

References

Additional Reading

Chapter 13 Homolytic Pathways in the Reactions of Alkylmetals

I. Introduction

II. ß-Elimination of Alkyl Ligands

III. Reductive Coupling of Alkyl Ligands

IV. a-Elimination of Alkyl Ligands

V. Hydrogen Transfer to Alkyl Ligands

VI. Displacement Reactions in Alkylmetals

References

Chapter 14 Catalytic Processes for the Formation of Carbon-Carbon Bonds

I. Alkyl Coupling versus Alkyl Disproportionation in Kharasch Reactions

II. Copper Catalysis in the Cross Coupling of Alkyl Groups

III. Iron Catalysis in the Cross Coupling of Alkenyl Halides

IV. Nickel Catalysis in Cross-Coupling Reactions of Aryl and Vinyl Halides

V. Cross Coupling with Allylic Groups

VI. Alkyl Coupling by Insertion into Carbon-Carbon Multiple Bonds

VII. Palladium and Rhodium Catalysis of Homo Coupling

VIII. Carbonylation Reactions

IX. Cyclooligomerization of Olefins and Acetylenes

References

Additional Reading

Part Three Charge Transfer Interactions of Organometals

Chapter 15 Organometals as Electron Donors

I. Electron Transfer Processes

II. Charge Transfer Interactions

III. Ionization Potentials of Organometals

IV. Charge Transfer Spectra of Organometals with Tetracyanoethylene

V. Charge Transfer Interactions Leading to Electron Transfer

VI. Operational Distinction between Electron Transfer and Charge Transfer Processes in Reactions of Organometals

References

Additional Reading

Chapter 16 Electron Transfer and Charge Transfer Processes in the Cleavage of Alkylmetals

I. Electron Transfer Cleavage of Organometals with Hexachloroiridate(IV)

II. Charge Transfer Addition of Organometals to Tetracyanoethylene

III. Other Reactions of Organometals Involving Electron Transfer or Charge Transfer

IV. Charge Transfer, Electron Transfer, and Concerted Processes for the Reactions of Organometals

References

Additional Reading

Chapter 17 Charge Transfer Interactions in the Reactions of Organometals with Acceptors

I. Introduction

II. Reactions of Organometals with Organic Halides

III. Reactions of Organometals with Quinones

IV. Grignard Reagents with Carbonyl Compounds

V. Reactions of Organometals with Oxygen and Peroxides

VI. Reactions of Organometals with Nitro Compounds

References

Additional Reading

Chapter 18 Reactions of Organometals with Electrophiles

I. Introduction

II. Cleavage Reactions of Electrophiles

III. Insertion Reactions of Electrophiles

IV. Delineation of Electrophilic and Electron Transfer Mechanisms: A Summing Up

References

Additional Reading

Epilogue

Index