The second edition of Organometallic Compounds (1960) was used not only by specialists but also as an undergraduate textbook. The third edition, recently published in two volumes, is about three times the length of the second and contains considerably more factual material than is appropriate for a student textbook. Therefore we believe that a shorter treatment would be welcome. In planning this book the authors have emphasized matters more of prin ciple than of detail, and have included in the first two chapters some general discussion of the properties and syntheses of organometallic compounds that is not to be found in the larger work. Some aspects of the organic chemistry of arsenic, and of silicon with particular reference to silicone polymers, are also included. Most university teachers of chemistry are becoming seriously concerned about the relentless increase in the amount and complexity of the material that is squeezed into undergraduate chemistry courses. With this in mind the authors have tried to cut detail to a minimum, but readers will find that the relative amount presented varies considerably between the various topics discussed. In general the treatment is more extensive than usual only if either or both of these conditions are met: (1), the subject has significant bearing on other major branches of chemistry including im portant industrial processes; (2), the topic is commonly misunderstood or found to be confusing.
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Dateigröße
ISBN-13
978-94-010-9681-2 (9789401096812)
DOI
10.1007/978-94-010-9681-2
Schweitzer Klassifikation
1. General Survey.- Historical background.- Properties.- Classification of organometallic compounds by bond type.- Covalent, two-centre, two-electron bonds.- Ionic organometallic compounds.- Electron-deficient (multicentre bonded) compounds.- Cluster compounds.- Occurrence of bond type in organo-transition metal complexes.- Availability of electron orbitals in metals and metalloids.- The stability of organometallic compounds.- 2. Methods of Formation of Metal-Carbon Bonds of the Main Group Elements.- The reaction between a metal and an organic halogen compound.- Metal exchange:-the reaction between a metal and an organometallic compound of another metal.- Reactions of organometallic compounds with metal halides.- Insertion of olefins and acetylenes into metal-hydrogen bonds.- Formation of metal-carbon bonds by other insertion reactions.- Reactions of diazo compounds.- Decarboxylation of heavy B-metal salts.- Mercuration and thallation of aromatic compounds.- Mercuration of olefins and acetylenes.- 3. Organometallic Compounds of Elements of the First Three Periodic Groups.- Structural aspects of the metal alkyls.- Preparative aspects.- 4. Organometallic Compounds of Elements of Main Groups IV and V.- Group IVB elements.- Silicones.- Group VB elements.- 5. Organometallic Compounds of the d-Block Transition Elements: Classification of Ligands and Theories of Bonding.- Classification of ligands.- The 18-electron rule.- Bonding in organometallic ?-complexes.- The bonding of other unsaturated hydrocarbons to transition metals.- 6. Preparation of Organo-Transition Metal Compounds.- General considerations.- Preparative routes.- Substitution by organometallic derivatives of main group elements.- Substition using organometallic derivatives of the transition elements : ligandtransfer.- From complex transition metal anions and halides.- Unexpected products.- 7. Reactions and Structures of Organometallic Compounds of the Transition Elements.- One-electron ligands.- Two-electron ligands.- Three-electron ligands: ?-allyl and ?-enyl complexes.- Four electron (diene) ligands.- Five-electron (dienyl) ligands.- Six-electron ligands.- Transition metal complexes containing ?-bonded heterocyclic ligands.- Seven-electron ligands.- Cyclo-octatetraene complexes.- 8. The Organic Chemistry of Ferrocene and Related Compounds.- The aromatic character of cyclic CnHn
ligands in transition metal complexes.- Aromatic properties of co-ordinated ligands.- Some mechanisms of electrophilic substitution.- Some particular reactions.- The interaction of the iron atom with ring substituents: ?-carbonium ion stabilization.- 9. Organometallic Complexes Formed from Acetylenes.- Mono-acetylene complexes.- Bisacetylene mononuclear complexes.- Trisacetylene complexes.- 10. The Role of Organotransition Metal Complexes in Some Catalytic Reactions.- Olefin isomerisation.- Homogeneous hydrogenation of olefins.- The oxidation of ethylene to acetaldehyde.- The trimerization of butadiene and related reactions catalyzed by some ?-allyl metal complexes.- Hydroformylation and related carbonylation reactions.- Catalytic conversation of acetylenes to ?? unsaturated acids in the presence of nickel carbonyl (Reppe process).- Vitamin B12 chemistry and related topics.- Nitrogen fixation.
