摘要：

Homogeneous Carbon Monoxide Hydrogenation.- 1. Stoichiometric CO Reduction (Model Reactions).- 1.1. CO Coordination.- 1.2. CO Activation (Scission and CH Bond Formation).- 1.2.1. CO Activation via Formyl Complexes.- 1.2.2. CO Activation via Hydroxymethyl, Hydroxymethylene Intermediates.- 1.2.3. CO Activation via Carbide, Carbyne, Carbene Intermediates.- 1.3. Formation of C1+ Species (Growth Products).- 1.3.1. Growth by Metal-C-C Bond Formation.- 1.3.2. Growth by Metal-O-C Bond Formation.- 1.3.3. Growth by Aldehydes as Intermediates.- 2. Catalytic Homogeneous Reduction of Carbon Monoxide.- 2.1. Reduction of CO with Reducing Agents Other than Molecular Hydrogen.- 2.2. Direct Reduction of CO with Hydrogen.- References.- FischerTropsch Synthesis.- 1. Introduction.- 2. Historic Developments in Heterogeneous Carbon Monoxide Hydrogenation.- 3. Technical Realization of the Fischer-Tropsch Synthesis.- 3.1. Types of Industrial Reactors.- 3.2. Integrated Structures of Production Plants.- 4. Basic Features of the Fischer-Tropsch Reaction.- 4.1. Stoichiometry.- 4.2. Thermodynamics.- 4.3. Molecular Weight Distribution of Products.- 4.4. Catalysts.- 4.4.1. Catalyst Metals.- 4.4.2. Promoters.- 4.4.3. Supports.- 4.4.4. Poisons.- 4.4.5. Preparation, Activation and Performance of Catalysts.- 4.5. Surface Species.- 5. Product Selectivity Control.- 5.1. Control of Molecular Weight Distribution.- 5.2. Selective Manufacture of Olefins.- 5.3. Selective Manufacture of Alcohols.- 6. Mechanistic Considerations.- 6.1. The Carbide Mechanism.- 6.2. The Hydroxycarbene Mechanism.- 6.3. Carbon Monoxide Insertion Mechanisms.- 6.4. Evaluation of the Proposed Mechanisms.- 7. Conclusions.- References.- Methanol Building Block for Chemicals.- 1. Mechanism of CO Reduction to Methanol.- 2. Future Use of Methanol.- 2.1. Methanol: Raw Material for the Chemical Industry.- 2.1.1. Base Chemicals from Methanol.- 2.1.1.1. Olefins and aromatics.- 2.1.1.2. Generation of pure hydrogen.- 2.1.1.3. Generation of pure CO.- 2.1.1.4. Synthesis of styrene.- 2.1.2. Fine Chemicals from Methanol.- 2.1.2.1. Acetic anhydride.- 2.1.2.2. Vinylacetate.- 2.1.2.3. Ethylene glycol.- 2.1.2.4. Methyl methacrylate.- 2.1.2.5. Methyl formate.- References.- The Homologation of Methanol.- 1. Introduction.- 1.1. Principle of the Homologation Reaction.- 1.2. Potential Use of Methanol Homologation.- 2. Cobalt-Catalyzed Methanol Homologation.- 2.1. Historic Developments and Recent Progress.- 2.2. Parameters Controlling the Homologation Reaction.- 2.2.1. Influence of Catalyst Composition.- 2.2.1.1. Nature of the cobalt compound.- 2.2.1.2. Promoters.- 2.2.1.3. Ligands.- 2.2.1.4. Cometals as hydrogenation catalysts.- 2.2.2. Influence of Reaction Conditions.- 2.2.2.1. Solvents.- 2.2.2.2. CO/H2 ratio.- 2.2.2.3. Syngas pressure.- 2.2.2.4. Reaction temperature.- 2.2.2.5 Reaction time.- 2.3. Possible Reaction Mechanisms.- 2.3.1. Nonpromoted Cobalt Catalysts.- 2.3.2. Iodine-Promoted Cobalt Catalysts.- 2.3.3. Hydrogenation of Acetaldehyde to Ethanol.- 2.3.4. Side-product Formation.- 3. Other Catalyst Metals.- 3.1. Iron Catalysts.- 3.2. Ruthenium Catalysts.- 3.3. Rhodium Catalysts.- 4. Conclusions.- References.- Hydroformylation and Carbonylation Reactions.- 1. Hydroformylation and Carbonylation of Unsaturated Organic Substrates.- 1.1. Introduction.- 1.2. Reppe-Type Chemistry.- 1.2.1. Alkyne Carbonylation.- 1.2.2. Alkene Carbonylation.- 1.3. The Hydroformylation Reaction.- 1.3.1. Unmodified Cobalt Carbonyl Systems.- 1.3.2. Phosphine-Modified Cobalt Carbonyl Systems.- 1.3.3. Rhodium Catalysts.- 1.4. General Mechanistic Implications.- 1.5. Carbonylation in Acidic Conditions.- 2. Carbonylation Under Oxidative Conditions.- 2.1. Introduction.- 2.2. The Synthesis of Oxalates.- 2.3. The Synthesis of Acrylates and Related Derivatives.- 2.4. The Synthesis of Carbonates.- References.- Activation of Carbon Dioxide via Coordination to Transition Metal Complexes.- 1. Introduction.- 2. Insertion of Carbon Dioxide into Transition Metal Complexes.- 2.1. Insertion into M-C Bonds.- 2.2. Insertion into M-H Bonds.- 2.3. Insertio

展开