In recent years, the liquid phase oxidation of organic substrates using transition metal compounds as catalysts has become a profitable means of obtaining industrially important chemicals. Millions of tons of valuable petrochemicals are produced in this manner annually [1]. Typical examples of such processes are the production of vinyl acetate or acetaldehyde via the Wacker process, equations (1) and (2); the Mid Century process for the oxidation of methyl aromatics, such as p-xylene to tereph thalic acid, equation (3); and the production of propylene oxide from propylene using alkyl hydroperoxides, equation (4). PdCI , CuCI 2 2 (1) CH2 = CH2 + 1/2 O2 -H 0 ~ CH3CHO 2 (2) Co(OAcjz ~ (3) (4) The vast majority of liquid phase transition metal catalyzed oxidations of organic compounds fall into these three broad categories: (a) free radical autoxidation reactions, (b) reactions involving nucleophilic attack on coordinated substrate such as the Wacker process, or (c) metal catalyzed reactions of organic substrates with hydroperoxides. Of these three classes of oxidations only the first represents the actual interaction of dioxygen with an organic substrate. The function of oxygen in the Wacker process is simply to re-oxidize the catalyst after each cycle [2].
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ISBN-13
978-90-277-0786-4 (9789027707864)
DOI
10.1007/978-94-010-1199-0
Schweitzer Klassifikation
of Volume 3.- Transition Metal Complexes as Catalysts for the Addition of Oxygen to Reactive Organic Substrates.- 1. Introduction.- 2. Structure and Bonding in Dioxygen Complexes.- 3. Properties of Coordinated Dioxygen.- 4. Formation and Stability of Dioxygen Complexes.- 5. Transfer of Coordinated Dioxygen to Reactive Substrates.- 6. Oxidation of Coordinated Ligands.- 7. Catalytic Oxidation Reactions.- 8. Catalytic Oxidation of Phosphines to Phosphine Oxides.- 9. Oxidation of Arsines to Arsine Oxides.- 10. Oxidation of Sulfides and Sulfoxides.- 11. Oxidation of Nitrogen Compounds.- 12. Carbon Monoxide.- 13. Aldehydes.- 14. Ketones.- 15. Alcohols.- 16. Oxidation of Olefins.- 17. Concluding Remarks.- 18. References.- Structure and Electronic Relations Between Molecular Clusters and Small Particles: An Essay to the Understanding of Very Dispersed Metals.- 1. Introduction.- 2. An Analysis of Size Range: A method of Finding an Overlap Between Very Small Particles and Molecular Clusters.- 3. Characterisation of Very Small Particles and of Molecular Clusters.- 4. Geometric Aspects of the Relation Between Very Small Particles and Molecular Clusters.- 5. Electronic Structures of Molecular Clusters and of Very Small Particles.- 6. Metal-Metal Bond Characteristics in Very Small Particles and Molecular Clusters.- 7. Electronic Aspects.- 8. Conclusion.- 9. References.- Asymmetric Hydrosilylation by Means of Homogeneous Catalysts with Chiral Ligands.- 1. Introduction.- 2. Hydrosilylation Using Homogeneous Catalysts.- 3. Catalytic Asymmetric Hydrosilylation of Prochiral Olefins.- 4. Selective Reduction of Carbonyl Compound via Hydrosilylation Catalyzed by a Rhodium(I) Complex.- 5. Asymmetric Reduction of Ketones via Catalytic Hydrosilylation.- 6. Asymmetric Reduction ofCarbon-Nitrogen Double Bond via Hydro-silylation.- 7. Asymmetric Synthesis of Bifunctional Organosilicon Compounds via Hydrosilylation.- 8. Conclusion.- 9. Acknowledgments.- 10. Abbreviations for Ligand Names.- 11. References.
