Homogeneous catalysis using transition metal complexes is an area of research that has grown enormously in recent years. Many amazing catalytic discoveries have been reported by researchers both in industry and in academia. Homogeneous Catalysis: Understanding the Art gives real insight in the many new and old reactions of importance. It is based on the author's extensive experience in both teaching and industrial practice. Each chapter starts with the basic knowledge and ends with up-to-date concepts. The focus of this book is on concepts, but many key industrial processes and applications that are important in the laboratory synthesis of organic chemicals are used as examples. The full range of topics is covered, such as fine chemicals, bulk chemicals, polymers, high-tech polymers, pharmaceuticals, but also important techniques and reaction types among other aspects. For a few reactions the process schemes, environmental concerns and safety aspects are included, to encourage catalyst researchers to think about these topics at an early stage of their projects and to communicate with chemical engineers, customers and the end-users. Homogeneous Catalysis: Understanding the Art provi
Sprache
Verlagsort
Zielgruppe
Für höhere Schule und Studium
Für Beruf und Forschung
ISBN-13
978-1-4020-2000-1 (9781402020001)
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Schweitzer Klassifikation
Preface; Acknowlegements; 1: Introduction; 1.1. Catalysis; 1.2. Homogeneous catalysis; 1.3. Histrical notes on homogeneous catalysis; 1.4. Characterization of the catalyst; 1.5. Ligand effects; 1.6. Ligands according to donor atoms; 2: Elementary Steps; 2.1. Creation of a "vacant" site and co-ordination of the substrate; 2.2. Insertion versus migration; 2.3. b-Elimination and de-insertion; 2.4. Oxidative addition; 2.5. Reductive elimination; 2.6. a-Elimination reactions; 2.7. Cycloaddition reactions involving a metal; 2.8. Activation of a substrate toward nucleophilic attack; 2.9. -Bond metathesis; 2.10. Dihydrogen activation; 2.11. Activation by Lewis acids; 2.12. Carbon-to-phosphorus bond breaking; 2.13. Carbon-to-sulfur bond breaking; 2.14. Radical reactions; 3: Kinetics; 3.1. Introduction; 3.2. Two-step reaction scheme; 3.3. Simplifications of the rate equation and the rete-determining step; 3.4. Determining the selectivity; 3.5. Collection of rate data; 3.6. Irregularities in catalysis; 4: Hydrogenation; 4.1. Wilkinson's catalyst; 4.2. Asymmetric hydrogenation; 4.3. Overview of chiral bidentate ligands; 4.4. Monodentate ligands; 4.5. Non-linear effects; 4.6. Hydrogen transfer; 5: Isomerisation; 5.1. Hydrogen shifts; 5.2. Asymmetric isomerisation; 5.3. Oxygen shifts; 6: Carbonylation of Methanol and Methyl Acetate; 6.1. Acetic acid; 6.2. Process scheme Monsanto process; 6.3. Acetic anhydride; 6.4. Other systems; 7: Cobalt Catalysed Hydroformylation; 7.1. Introduction; 7.2. Thermodynamics; 7.3. Cobalt catalysed processes; 7.4. Cobalt catalysed processes for higher alkenes; 7.5. Kuhlmann cobalt hydroformylation process; 7.6. Phosphine modified cobalt catalysts: the shell process; 7.7. Cobalt carbonyl phosphine complexes; 8: Rhodium Catalysed Hydroformylation; 8.1. Introduction; 8.2. Triphenylphosphine as the ligand; 8.3. Diphosphines as ligands; 8.4. Phosphites as ligands; 8.5. Diphosphites; 8.6. Asymmetric hydroformylation; 9: Alkene Oligomerisation; 9.1. Introduction; 9.2. Shell-higher-olefins-process; 9.3. Ethene trimerisation; 9.4. Other alkene oligomerisation reactions; 10: Propene Polymerisation; 10.1. Introduction to polymer chemistry; 10.2. Mechanistic investigations; 10.3. Analysis by 13CNMR spectroscopy; 10.4. The development of metallocene catalysts; 10.5. Agostic interactions; 10.6. The effect of dihydrogen; 10.7. Further work using propene and other alkenes; 10.8. Non-metallocene ETM catalysts; 10.9. Late transition metal catalysts; 11: Hydrocyanation of Alkenes; 11.1. The adiponitrile process; 11.2. Ligand effects; 12: Palladium Catalysed Carbonylations of Alkenes; 12.1. Introduction; 12.2. Polyketone; 12.3. Ligand effects on chain length; 12.4. Ethene/propene/CO terpolymers; 12.5. Stereoselective styrene/CO terpolymers; 13: Palladium Catalysed Cross-Coupling Reactions; 13.1. Introduction; 13.2. Allylic reaction; 13.3. Heck reaction; 13.4. Cross-coupling reacti
