S. Olivé

The Chemistry of the Catalyzed Hydrogenation of Carbon Monoxide

1 Introduction.- 1.1 References.- 2 Transition Metal-Hydrogen Interactions.- 2.1 Reaction of Hydrogen with Transition Metal Complexes and Surfaces.- 2.2 Metal-Hydrogen Bond Energy.- 2.3 Different Types of Metal-Hydrogen Bonding and the M-H Bond Length.- 2.4 Polarity of the M-H Bond.- 2.5 Mobility of Hydrogen Ligands.- 2.6 Conclusion.- 2.7 References.- 3 Transition Metal-Carbon Monoxide Interactions.- 3.1 The CO Molecule.- 3.2 Coordination Chemistry of CO in Molecular Complexes and Clusters.- 3.3 Molecular Carbon Monoxide on Metal Surfaces.- 3.4 CO Dissociation on Metal Surfaces.- 3.5 Conclusion.- 3.6 References.- 4 Non-Catalytic Interaction of CO with H2.- 4.1 On Metal Surfaces.- 4.2 CO/H2 Interaction in Transition Metal Complexes.- 4.2.1 Hydridocarbonyl Complexes.- 4.2.2 Formyl Complexes.- 4.2.3 Formaldehyde Complexes.- 4.2.4 A Methoxy Complex.- 4.2.5 Carbide Complexes.- 4.3 Conclusions.- 4.4 References.- 5 Key Reactions in Catalysis.- 5.1 Oxidative Addition.- 5.2 Reductive Elimination.- 5.2.1 Intramolecular Reductive Elimination.- 5.2.2 Intermolecular Reductive Elimination.- 5.3 Migratory Insertion Reactions.- 5.3.1 CO Insertion into Metal-Alkyl Bonds.- 5.3.2 Alkyl Migration versus CO Migration.- 5.3.3 Promotion of Migratory CO Insertion.- 5.3.4 Absence of Acyl-to-CO Migration.- 5.3.5 CO Insertion into Metal-H Bonds.- 5.3.6 Migratory Insertions involving Carbene Ligands.- 5.3.7 Olefin Insertion.- 5.3.8 Coinsertion of Ethylene and CO.- 5.3.9 Insertion of Formaldehyde.- 5.4 Hydrogen Eliminiation Reactions.- 5.4.1 ?-Hydrogen Elimination.- 5.4.2 ?-Elimination of Hydrogen.- 5.4.3 ?- and ?-Elimination of Hydrogen.- 5.5 Ligand Influences.- 5.5.1 In Molecular Complexes.- 5.5.2 On Metal Surfaces.- 5.6 Conclusion.- 5.7 References.- 6 Catalysts and Supports.- 6.1 Molecular Complexes and Metal Surfaces - Analogies and Differences.- 6.2 Supported Metal Catalysts.- 6.2.1 Metals and Supports Used for CO Hydrogenation.- 6.2.2 Metal-Support Interactions.- 6.2.3 Steric Constraints in Zeolites.- 6.3 Conclusions.- 6.4 References.- 7 Methanation.- 7.1 Carbide Mechanism.- 7.2 CO Insertion Mechanism.- 7.3 Inverse H/D Isotope Effects.- 7.4 Conclusion.- 7.5 References.- 8 Methanol from CO + H2.- 8.1 Nondissociative Incorporation of CO.- 8.2 Homogeneous Methanol Formation.- 8.3 Methanol Synthesis with Supported Noble Metal Catalysts.- 8.4 Synergism in the Cu/ZnO Catalyst.- 8.5 Conclusions.- 8.6 References.- 9 Fischer-Tropsch Synthesis.- 9.1 Early Developments and Present State of Commercial Fischer-Tropsch Synthesis.- 9.2 The Products of the FT Synthesis.- 9.2.1 Primary Products.- 9.2.2 Secondary Reactions of the ?-Olefins.- 9.2.3 Modified FT Synthesis.- 9.3 Distribution of Molecular Weights.- 9.3.1 The Schulz-Flory Distribution Function.- 9.3.2 Experimental Molecular Weight Distributions.- 9.4 Kinetics and Thermodynamics of the FT Reaction.- 9.5 Reaction Mechanism.- 9.5.1 Suggested Mechanisms.- 9.5.2 The Carbide Theory in the Light of Homogeneous Coordination Chemistry.- 9.5.3 Details and Support for the CO Insertion Mechanism.- 9.5.4 The Chain Initiating Step.- 9.5.5 Secondary Reactions.- 9.6 Influence of the Dispersity of Metal Centers.- 9.7 Influence of the Temperature and Pressure.- 9.7.1 Hydrocarbons versus Oxygenates.- 9.7.2 The Particular Case of Ruthenium Catalysts.- 9.8 The Role of Alkali Promoters.- 9.9 Product Selectivity.- 9.9.1 Consequences of the Schulz-Flory Molecular Weight Distribution.- 9.9.2 Deviations from the Schulz-Flory Distribution.- 9.10 Conclusion.- 9.11 References.- 10 Homogeneous CO Hydrogenation.- 10.1 Hydroformylation of Olefins (Oxo Reaction).- 10.2 Hydroformylation of Formaldehyde.- 10.3 Polyalcohols from CO + H2, and Related Homogeneous Syntheses.- 10.4 Conclusion.- 10.5 References.- 11 Methanol as Raw Material.- 11.1 Carbonylation of Methanol (Acetic Acid Synthesis)..- 11.2 Methanol Homologation.- 11.3 Hydrocarbons from Methanol Dehydration and Condensation.- 11.4 Conclusion.- 11.5 References.- 12 Attempt of a Unified View.- 12.1 References.- 13 Subject Index.

Molecular interactions and macroscopic properties of polyacrylonitrile and model substances

The relationships between intra- and intermolecular forces in polyacrylonitrile on the one hand, and the macroscopic behavior of the polymer and fibers thereof on the other, are reviewed. Characteristic properties such as the very high polymerization rate constant in water, the dissolution of the polymer in concentrated inorganic salt solutions, the high melting point, the strong depression of melting point and glass transition temperature by water, the plasticization by polar additives, etc., are traced back to their molecular origins, in particular to the strong intra- and intermolecular noncovalent bonding caused by the highly polar nitrile group. The effects of dipole-dipole interaction, hydrogen bonding and electron-donor-acceptor complex formation are discussed separately.

Reactions of carbon monoxide with transition metal-carbon bonds

SummaryInsertions of carbon monoxide into transition metal-carbon bonds are among the most selective methods for the catalytic introduction of oxygen into organic compounds. A variety of processes are known today and most of them are of great industrial importance. Depending on the nature of the organic substrate, the catalyst and additional reaction components products range from aldehydes, alcohols, and acids to esters, anhydrides, acid chlorides, amides etc. An attempt is made here to show that all these reactions proceed by similar mechanisms.

Key Polymers Properties and Performance

Editorial.- The preparation, structure and properties of ultra-high modulus flexible polymers.- Synthetic ion-exchange resins.- The miscibility of high polymers: The role of specific interactions.- Flammability of polymeric materials.

Analysis/reactions/morphology

Small angle neutron scattering from block copolymers.- Formation of living propagating polymer radicals in microspheres and their use in the synthesis of block copolymers.- Polymerization of butadiene and butadiyne (diacetylene) derivatives in layer structures.- Kinetics and mechanisms of polyesterifications II. Reactions of diacids with diepoxides.- Swelling equilibrium studies of elastomeric network structures.

Solar energy - phase transfer catalysis - transport processes

Solar energy conversion by functional polymers.- Polymer-supported phase transfer catalysts: Reaction mechanisms.- Rapid polymer transport in concentrated solutions.