Palladium Catalyzed Oxidation of Hydrocarbons

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Dezember 1979



The field of organometallic chemistry has emerged over the last twenty-five years or so to become one of the most important areas of chemistry, and there are no signs of abatement in the intense current interest in the subject, particularly in terms of its proven and potential application in catalytic reactions involving hydrocarbons. The development of the organometallic/ catalysis area has resulted in no small way from many contributions from researchers investigating palladium systems. Even to the well-initiated, there seems a bewildering and diverse variety of organic reactions that are promoted by palladium(II) salts and complexes. Such homogeneous reactions include oxidative and nonoxidative coupling of substrates such as olefins, dienes, acetylenes, and aromatics; and various isomerization, disproportionation, hydrogenation, dehydrogenation, car­ bonylation and decarbonylation reactions, as well as reactions involving formation of bonds between carbon and halogen, nitrogen, sulfur, and silicon. The books by Peter M. Maitlis - The Organic Chemistry of Palladium, Volumes I, II, Academic Press, 1971 - serve to classify and identify the wide variety of reactions, and access to the vast literature is available through these volumes and more recent reviews, including those of J. Tsuji [Accounts Chem. Res. , 6, 8 (1973); Adv. in Organometal. , 17, 141 (1979)], R. F. Heck [Adv. in Catat. , 26, 323 (1977)], and ones by Henry [Accounts Chem. Res. , 6, 16 (1973); Adv. in Organometal. , 13, 363 (1975)]. F. R. Hartley's book - The Chemistry of Platinum and Palladium, App!. Sci. Pub!.


I Introduction and Background.- A. General and Historical.- B. Inorganic Chemistry of Palladium.
- 1. Pd(0).
- 2. Pd(I).
- 3. Pd(II).
- a. Stable Compounds.
- b. Equilibrium in Solution.- (i) Aqueous Solution.- (ii) Acetic Acid.- (iii) Acetonitrile.- (iv) Methanol and other Solvents.
- 4. Pd(IV).- C. Organometallic Chemistry of Palladium.
- 1. Alkyls, Vinyls and Aryls.
- 2. Compounds of Palladium with Unsaturated Carbon Containing Ligands.
- a. General.
- b. Pd(0).
- c. Pd(I).
- d. Pd(II).- (i) Olefin ?-Complexes.- (ii) ?-Acetylene Complexes.- (iii) ?-Allyl Complexes.- (iv) Cyclobutadiene and other C4 Systems.- (v) Cyclopentadienyl Complexes.- D. The Two Basic Reactions of Catalysis and Examples of Each in Stable Palladium Organometallic Chemistry.
- 1. General.
- 2. The Oxidative Addition Reaction.
- 3. The Insertion Reaction.- II Oxidation of Monoolefins.- A. General.- B. Formation of Aldehydes and Ketones.
- 1. Reaction Schemes.
- 2. Mechanism.
- a. Effect of Ionic Strength.
- b. Deuterium Labeling Experiments.
- c. Kinetic Isotope Effects.
- d. Ionic Strength Effects.
- e. Exchange Studies.
- f. Oxidation by Pd(II) Complexed to Di- and Triamines.- C. Production of Esters.
- 1. Introduction.
- 2. Oxidation in the Absence of Added Oxidants.
- 3. Oxidation in the Presence of other Oxidants.
- 4. Mechanism.
- a. Unsaturated Ester Formation.
- b. Saturated Ester Formation.- D. Production of Ethers and Acetals in Alcohols.
- 1. Reaction Schemes.
- 2. Mechanism.- E. Formation of Carbon-Carbon Bonds.
- 1. Introduction.
- 2. Olefin Arylation Reaction.
- a. Reaction Schemes.
- b. Mechanism.
- 3. Aliphatic and Olefinic Carbon-Carbon Bond Formation.
- a. Addition of Pd(II)-Carbon Bonds across Olefinic Substrates.
- b. Olefin Coupling Reaction.
- c. Nonoxidative Dimerization.
- 4. Carbonylation Reaction with CO.- F. Formation of Carbon-Nitrogen Bonds.- G. Formation of Carbon-Halogen Bonds.- H. Formation of Carbon-Sulfur Bonds.- I. Formation of Carbon-Silicon Bonds.- J. Reaction of Monoolefins with (Ph3P)2PdO2.- K. Formation of Nitrates.- III Reaction of Dienes and Polyenes.- A. Nonconjugated Dienes.
- 1. Stable Adducts.
- 2. Catalytic Reactions.- B. Conjugated Diolefins.
- 1. 1,3-Diene Reactions.
- a. Oxidation without Oligomerization.
- b. Addition with Telomerization.
- c. Cocyclization Reactions with Heteropolar Double Bonds.
- d. Dimerization and Polymerization of 1,3-Dienes without Addition of Nucleophile.
- e. Mechanisms of 1,3-Diene Reactions.
- 2. Reactions of 1,2-Dienes.- IV ?-Allyl Complexes.- A. General.- B. Formation and Structure.- C. Reactions of ?-Allyl Complexes.
- 1. Aqueous Solutions.
- 2. Acetic Acid Solvent.
- 3. Formation of Carbon-Carbon Bonds.
- 4. Other Decomposition Reactions.- V Reactions of Acetylenes.- A. General.- B. Oxidative Reactions.- C. Nonoxidative Reactions.- VI Reactions of Aromatic Compounds.- A. Stable Palladium(II) Aryls.- B. Formation of Carbon-Oxygen Bonds: Aromatic Acetoxylation.- C. Formation of Carbon-Carbon Bonds.
- 1. Aromatic Coupling.
- 2. Carbonylation Reactions.
- 3. Miscellaneous Aromatic Carbon-Carbon Formation Reactions.- D. Formation of other Aromatic Bonds.- E. Mechanism of Aromatic Substitution Reactions.- VII Miscellaneous Reactions.- A. Benzylic Oxidation.- B. Oxidative Dehydrogenation.- C. Reactions of Carbonyl-Containing Compounds.
- 1. Aldehydes and Ketones.
- 2. Quinone.
- 3. Carboxylic Acids and Acid Chlorides.- D. Reaction of C-O Bonds.
- 1. Alcohols.
- 2. Oxazines.
- 3. Hydroperoxides.
- 4. Lactones.
- 5. CO2.- E. Nitrogen-Containing Functional Groups.
- 1. Amines.
- 2. Nitro Compounds.
- 3. Reaction of Groups Containing ?C=N?.
- 4. Reactions of ?C?N Groups.
- 5. Miscellaneous N-Containing Groups.- F. Oxidation of Cyclopropanes.- G. Miscellaneous CO Reactions.- H. S and Si Containing Reactants.- Indexes.


EAN: 9789027709868
ISBN: 9027709866
Untertitel: 1980. Auflage. Book. Sprache: Englisch.
Verlag: Springer
Erscheinungsdatum: Dezember 1979
Seitenanzahl: 456 Seiten
Format: gebunden
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