Aspects of homogeneous catalysis : a series of advances


Aspects of homogeneous catalysis : a series of advances

edited by Renato Ugo

Carlo Manfredi, 1970-

  • vol. 1
  • vol. 2
  • vol. 3
  • vol. 4
  • vol. 5
  • vol. 6
  • vol. 7

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v. 2-6: Published by D. Reidel (Dordrecht)

v. 7: Published by Kluwer Academic (Dordrecht)



vol. 7 ISBN 9780792308881


The literature contains tens of thousands of publications and patents devoted to the synthesis, characterization and processing of polymers. Despite the fact that there are more than one hundred elements, the majority of these publications and patents concern polymers with carbon backbones. Furthermore, the limited (by comparison) number of publications on polymers that contain elements other than carbon in their backbones are typically devoted to polymers based on silicon, especially those with Si-O bonds. This disparity is partially a consequence of the dearth of low cost organometallic feedstock chemicals potentially useful for polymer synthesis. It also derives from the lack of general synthetic techniques for the preparation of organometallic polymers. That is, by comparison with the numerous synthetic strategies available for the preparation of organic polymers, there are few such strategies available for synthesizing tractable, organometallic polymers. In recent years, commerical and military performance requirements have begun to challenge the performance limits of organic polymers. As such, researchers have turned to organometallic polymers as a possible means of exceeding these limits for a wide range of applications that include: (1) microelectronics processing (e.g. photoresists) [1]; (2) light weight batteries (conductors and semi-conductors) [2]; (3) non-linear optical devices [3] and, (4) high temperature structural materials (e.g. ceramic fiber processing) [4,5].


Large Transition Metal Clusters - Bridges between Homogeneous and Heterogeneous Catalysts?.- 1. Introduction.- 2. Large Clusters.- 3. Colloids.- 4. Supported Metal Particles.- 5. Large Clusters in Catalysis.- 6. Conclusions.- 7. References.- Transition Metal Catalyzed Synthesis of Organometallic Polymers.- 1. Introduction.- 2. Dehydrocoupling Reactions.- 3. Dehydrocoupling at Boron.- 4. Dehydrocoupling at Silicon.- 5. Si-H Self-Reaction Dehydrocoupling.- 6. Si-H Catalytic Reaction with E-H.- 7. Redistribution Reactions.- 8. Ring-Opening Catalysis.- 9. Future Directions.- 10. References.- Homogeneous Catalytic Hydrogenation of Aromatic Hydrocarbons and Heteroaromatic Nitrogen Compounds: Synthetic and Mechanistic Aspects.- 1. Introduction.- 2. Hydrogenation of Mono and Polynuclear Aromatic Hydrocarbons.- 3. Hydrogenation of Mono and Polynuclear Heteroaromatic Nitrogen Compounds.- 4. High Pressure Nuclear Magnetic Resonance Studies: The Mechanism of Quinoline Hydrogenation with Cp*Rh2+.- 5. Conclusions.- 6. Acknowledgement.- 7. References.- Surface Organometallic Chemistry on Oxides, on Zeolites and on Metals.- 1. Introduction.- 2. Basic Rules Governing the Reactivity of Organometallic Compounds with Surfaces of Inorganic Oxides.- 3. Some Elementary Steps in Heterogeneous Catalysis from Well Defined Surface Organometallic Fragments.- 4. Surface Organometallic Chemistry as a Tool for Tailor Made Catalysts: Preparation of Bimetallic Particles from Bimetallic (or Heteropolynuclear) Clusters of Group VIII Metals.- 5. Surface Organometallic Chemistry on Zeolites: a New Approach for the Control of the Pore Opening Size.- 6. Surface Organometallic Chemistry on Metals: New Generation of Bimetallic Catalysts Obtained by Reaction of Complexes of Main Group Elements with Group VIII Metals in Zero or Higher Oxidation State.- 7. Conclusion.- 8. References.

vol. 2 ISBN 9789027705228


of Volume 2.- Hydroformylation of Olefins with Carbonyl Derivates of the Noble Metals as Catalysts.- 1. Introduction.- 2. Comparison of the Activity of Group VIII Metals.- 3. Hydroformylation with Rhodium Complexes as Catalysts.- 4. Hydroformylation with Iridium Complexes as Catalysts.- 5. Hydroformylation with Ruthenium and Osmium Complexes as Catalysts.- 6. Hydroformylation with Palladium and Platinum Catalysts.- 7. Hydrogenation of Aldehydes with Carbonyl Derivatives of the Noble Metals as Catalysts.- 8. Recent Results.- 9. Conclusions.- 10. References.- Addition of hydrogen cyanide to mono-olefins catalyzed by transition metal complexes.- 1. Introduction and scope.- 2. Interaction of hydrogen cyanide with metal complexes.- 3. Hydrocyanation of non-activated olefins.- 4. The proposed mechanisms of hydrocyanation.- 5. Hydrocyanation of activated olefins.- 6. Recent results.- 7. Conclusion.- 8. References.- Nickel Catalyzed Syntheses of Methyl-Substituted Cyclic Olefins, an Example of Stepwise Carbon-Carbon Bond Formation Promoted by a Transition Metal Complex.- 1. Introduction.- 2. Cope Rearrangement of 1,5-dienes.- 3. Preparation of monomethyl derivatives by methylene insertion reaction (MIR).- 4. Preparation of dimethyl derivatives by MIR.- 5. Identification of isomers using the combination gas chromatography/mass spectrometry.- 6. Catalytic syntheses of mono and dimethyl substituted ring olefins.- 7. Mechanism of carbon-carbon bond formation promoted by low valent nickel catalysts.- 8. Some general aspects of carbon-carbon and carbon-hydrogen bond formation promoted by transition metals.- 9. References.- Dimerization of Acrylic Compounds.- 1. Introduction.- 2. Thermal and photo dimerization.- 3. Dimerization by alkali metal amalgams and direct electrolysis.- 4. Phosphine-catalyzed dimerization.- 5. Dimerization by transition metal complexes.- 6. Conclusion.- 7. References.

vol. 1 ISBN 9789027705488


of Volume 1.- Recent Advances in Homogeneous Hydrogenation of Carbon-Carbon Multiple Bonds.- 1. Introduction and scope.- 2. Basic reactions in homogeneous hydrogenation.- 3. Techniques for studying homogeneous hydrogenation.- 4. Cobaltous cyanide and related systems.- 5. Bi-metallic systems.- 6. Catalysts stabilised by tertiary phosphines.- 7. Hydrogenation catalysed by transition metal salts in polar media.- 8. Organometallic catalysts.- 9. Metal carbonyls.- 10. Miscellaneous hydrogenations.- 11. Recent Results.- 12. Summary.- 13. References.- Stereoselectivity in Organic Syntheses Involving Nickel-co-ordinated Intermediates.- 1. Introduction.- 2. Reactions of the triple bond.- 3. Conversion of the vinyl double bond into a trans double bond.- 4. Reactions of the allyl double bond.- 5. Stereoselective polymerisation.- 6. Utilisation of the stereoisomers.- 7. References.- Dimerization and Co-dimerization of Olefinic Compounds by Co-ordination Catalysis.- 1. General introduction.- 2. Transition metals as catalysts in dimerization of olefins.- 3. Appendix.- 4. References.- Selective Homogeneous Hydrogenation of Dienes and Polyenes to Monoenes.- 1. Introduction.- 2. General considerations.- 3. Complexes activating molecular hydrogen.- 4. First row transition metal complexes in the presence of cocatalytic agents.- 5. Non-transition metal hydrides.- 6. Summary and Conclusion.- 7. References.- Autor Index.

vol. 3 ISBN 9789027707864


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].


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 of Carbon-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.

vol. 4 ISBN 9789027711397


of Volume 4.- Metal-Catalysed Epoxidations of Olefins with Hydroperoxides.- 1. Introduction.- 2. Metal-Catalysed Epoxidations with Hydrogen Peroxide.- 3. Covalent Metal Peroxides as Epoxidizing Agents.- 4. Metal-Catalysed Epoxidations with Alkyl Hydroperoxides.- 5. Oxidation of other Functional Groups.- 6. Summary.- 7. Glossary of Non-Standard Abbreviations.- 8. References.- Homogeneous Catalytic Reduction of Carbonyl-, Azomethine-, and Nitro-Groups.- 1. Introduction.- 2. Reduction of the Carbonyl Group.- 3. Reduction of Schiff Bases.- 4. Reduction of Nitro-Compounds.- 5. Dihydrogen Evolution.- 6. Reaction Mechanisms.- 7. Conclusions.- 8. Abbreviations for Ligand Names.- 9. References.- Catalysis of Diolefin Reactions by ?3-Allyl Metal Complexes.- 1. Introduction.- 2. Allyl-MT Complexes: Bonding and Dynamic Behaviour.- 3. Oligomerisation, Co-Oligomerisation and Polymerisation of Diolefins.- 4. Relation between Catalyst Structure and Kinetic and Thermodynamic Controls of Butadiene Oligo- and Polymerisation Processes.- 5. Isomerisation of Diolefins.- 6. Heteroactivation of Diolefins.- 7. Conclusions.- 8. References.- Substrates and Phosphorus Ligands Used in Asymmetric Homogeneous Hydrogenations Catalysed by Rhodium Complexes.- 1. Introduction.- Table I: Chiral phosphines used as ligands in the rhodium-catalysed asymmetric hydrogenation.- Table 2: Substrates in the rhodium-catalysed asymmetric hydrogenation.- 2. References.

vol. 5 ISBN 9789027717382


1. INTRODUCTION Although quite spectacular results have been obtained in the last few decades in the field of homogeneous transition metal catalyzed transformations of olefins and alkynes [1], reactions which could lead to heterocycles have been partly neglected. An obvious reason for this is that substrates containing heteroatoms such as N, 0 or S could coordinate the metal and suppress the catalytic activity. Nevertheless, some interesting early examples of transition-metal-catalyzed syntheses of heterocyclic compounds have been reported and these have been reviewed by C. W. Bird [2] . More recently the incorporation of CO , which enables esters and lactones 2 to be synthesized from olefinic starting materials, has begun to attract attention (see, for example, ref. [3]). The dominant role of palladium as the catalyst for the formation of O-containing heterocycles has been suggested to be associated with the relatively low strength of the Pd-O bond. Among the first examples of a nitrogen-containing heterocycle to be formed by homogeneous catalysis is the triazine shown in Equation 1 which is the product of the trimerization of benzonitrile in the presence of iron penta carbonyl or Raney- nickel [4] .


of Volume 5.- Telomerization of Dienes by Homogeneous Transition Metal Catalysts.- 1. Introduction.- 2. Telomerization of Butadiene.- 3. Telomerization of Isoprene.- 4. Telomerization of Further 1,3-Dienes.- 5. Telomerization of 1,2-Dienes.- 6. Cotelomerizations.- 7. Acknowledgement.- 8. References.- The Cobalt-Catalyzed Synthesis of Pyridine and Its Derivatives.- 1. Introduction.- 2. Survey of the Organocobalt Catalysts.- 3. The Application of the Cobalt-Catalyzed Pyridine Synthesis.- 4. Experimental Details.- 5. Mechanistic Considerations.- 6. Experimental Optimization of the Catalytic Turnover Number.- 7. Synthesis of the Catalysts.- 8. Related Reactions.- 9. Acknowledgement.- 10. Glossary of Abbreviations.- 11. References.- Homogeneous Catalysis Using Iodide-Promoted Rhodium Catalysts.- 1. Introduction.- 2. Rhodium Iodocarbonyls.- 3. Catalysis of the Water Gas Shift Reaction.- 4. Alcohol Carbonylation.- 5. Carbonylation of Esters and Ethers.- 6. Reductive Carbonylation of Esters and Ethers.- 7. Hydrocarboxylation of Olefins.- 8. Hydrocarboxylation of Formaldehyde.- 9. Hydrogenolysis Reactions.- 10. Homologation of Carboxylic Acids.- 11. Heterogenisation of the Rh/I Catalyst.- 12. Conclusions.- 13. References.- Recent Developments in the Homogeneous Catalysis of the Water-Gas Shift Reaction.- 1. Introduction.- 2. Background.- 3. Chemistry of the WGSR Catalytic Cycles.- 4. Catalysis of the WGSR under Basic Conditions.- 5. Catalysis of the WGSR under Acidic or Neutral Conditions.- 6. References.- Homologation of Alcohols, Acids and Their Derivatives by CO + H2.- 1. Introduction.- 2. Homologation of Alcohols.- 3. Carbonylation and Homologation of Ethers.- 4. Homologation of Aldehydes.- 5. Homologation of Carboxylic Acids.- 6. Homologation of Carboxylic Acid Esters.- 7. Homologation Reactions with Heterogeneous Catalysts.- 8. Homologation Reactions with CO and H2O.- 9. Reaction Mechanism.- 10. Concluding Remarks.- 11. Addendum.- 12. Glossary of Abbreviations.- 13. References.

vol. 6 ISBN 9789027726384


Homogeneous Transition-Metal Catalysis in Molten Salts.- 1. Introduction.- 2. Synthesis Gas Processing.- 3. Short Chain Fatty Acids (SFA'S).- 4. Oxo Alcohols and Aldehydes.- 5. Fischer-Tropsch Chemistry.- 6. Olefin Hydrogenation.- 7. Chlorination and Oxidation.- 8. Conclusions.- Carbon Dioxide as Building Block for Fine Chemicals Synthesis by HomogeneousCatalysis.- 1. Alkenes.- 2. Dienes.- 3. Alkynes.- 4. Literature.- Metal Catalysed Deoxygenation Reactions by Carbon Monoxide of Nitroso andNitro Compounds.- 1. Introduction.- 2. Interaction of Nitroso and Nitro Compounds with the Metal Centre.- 3. Metal-assisted Stoichiometric Reactions in Nitroso and Nitro Compounds.- 4. Catalytic Reactions.- 5. Concluding Remarks.- 6. Glossary of Abbreviations.- 7. References.- Recent Aspects of Transition Metal Catalyzed Reactions of Carbenes in the Realm of Biologically Active Substances.- 1. Introduction.- 2. Generalities.- 3. Synthetic Applications.- 4. References.

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  • ISBN
    • 9027705488
    • 9027705224
    • 9027707863
    • 9027711399
    • 9027717389
    • 9027726388
    • 0792308883
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    25 cm
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