Catalysis in C1 Chemistry

Continuously increasing oil prices, a dwindling supply of petroleum, and the existence of extensive reserves of biomass, especially of coal, have given rise to a growing interest in generating CO/H from these sources. Catalytic reactions can 2 convert CO/H mixtures to useful hydrocarbons or hydrocarbon intermediates. 2 There is little doubt that petroleum will remain the backbone of the organic chemical industry for many years to come, yet there is great opportunity for CO as an alternative feedstock at times when it is needed. The loosely defined body of chemistry and technology contained in these areas of development has become known as C 1 chemistry, embracing many C 1 building blocks such as CH , CO/H , CO, CH OH, CO and HCN; still emphasis 4 2 3 2 rests on carbon monoxide. Academic research laboratories, oil and chemical companies are in the vanguard of C 1 chemistry. The Japanese Ministry of International Trade and Industry is sponsoring a seven-year program of 14 major chemical companies in C 1 chemistry aimed at developing new technology for making basic chemicals from CO and H2 . It is likely that C 1 chemistry will develop slowly but persistently and the future holds great potential.

Autorentext
Prof. em. Dr. Wilhelm Keim studierte Chemie in Münster und Saarbrücken und promovierte 1963 am MPI für Kohlenforschung, mehrjährige Tätigkeit bei Shell Development USA, 1973 Ernennung zum Ordentlichen Professor und Direktor des Instituts für Technische Chemie und Petrolchemie der RWTH Aachen. Forschungsschwerpunkt: Homogenen Katalyse und Verfahrensentwicklung. Auszeichnungen u.a. mit der Mittasch Medaille. Prof. Keim bekleidete zahlreiche Ehrenämter (Mitglied des Aufsichtsrats der Degussa-Hüls AG, Stellvertretender Vorsitzender des Vorstands der DECHEMA, Mitglied des Vorstands der GDCh, Stellvertretender Vorsitzender des Kuratoriums des Karl-Winnacker-Instituts, u.a.).

Inhalt
Homogeneous Carbon Monoxide Hydrogenation.- 1. Stoichiometric CO Reduction (Model Reactions).- 2. Catalytic Homogeneous Reduction of Carbon Monoxide.- References.- FischerTropsch Synthesis.- 1. Introduction.- 2. Historic Developments in Heterogeneous Carbon Monoxide Hydrogenation.- 3. Technical Realization of the Fischer-Tropsch Synthesis.- 4. Basic Features of the Fischer-Tropsch Reaction.- 5. Product Selectivity Control.- 6. Mechanistic Considerations.- 7. Conclusions.- References.- Methanol Building Block for Chemicals.- 1. Mechanism of CO Reduction to Methanol.- 2. Future Use of Methanol.- References.- The Homologation of Methanol.- 1. Introduction.- 2. Cobalt-Catalyzed Methanol Homologation.- 3. Other Catalyst Metals.- 4. Conclusions.- References.- Hydroformylation and Carbonylation Reactions.- 1. Hydroformylation and Carbonylation of Unsaturated Organic Substrates.- 2. Carbonylation Under Oxidative Conditions.- References.- Activation of Carbon Dioxide via Coordination to Transition Metal Complexes.- 1. Introduction.- 2. Insertion of Carbon Dioxide into Transition Metal Complexes.- 3. Transition Metal-Catalyzed Syntheses Involving Carbon Dioxide.- 4. Deoxygenation of CO2.- 5. Dimerization of CO2.- 6. Carbon Dioxide as a Cocatalyst in Homogeneous Catalysis.- 7. Conclusions.- 8. Glossary of Nonstandard Abbreviations.- References.- Hydrocyanation.- 1. Introduction.- 2. Reaction of HCN with Multiple Bonds.- 3. Applications of HCN in Organic Chemistry Other than Addition to Multiple Bonds.- 4. Physiological Properties of HCN and Safety.- References.- Methane.- 1. Methane.- 2. Alkanes.- References.- Carbenes.- 0. Introduction.- 1. The Structure of Carbenes.- 2. Reactivity of Carbenes.- 3. Regioselectivity of Carbenes.- 4. The Relative Stability of Spin States.- 5. The Generation of Carbenes.- 6. Carbene Metal Complexes.- 7. The Structure of Carbenoids.- 8. Carbenes in Fine-Chemical Synthesis.- 9. Carbenoids in Fine-Chemicals Synthesis.- 10. Mechanisms of Copper-Catalyzed Carbene Reactions.- 11. Catalysis by Metals Other than Copper.- 12. Synthetic Applications of Group VIII Transition Metal Complexes.- 13. Carbenoids in Industrial Process.- References.