Beschreibung
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.
Autorenporträt
Inhaltsangabe1. General Survey.- Historical background.- Properties.- Classification of organometallic compounds by bond type.- Covalent, two-centre, two-electron bonds.- Bond energies.- 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.- Thermal stability.- Stability to oxidation.- Stability to hydrolysis.- General features relating to stability:-filled shells of electrons.- 2. Methods of Formation of Metal-Carbon Bonds of the Main Group Elements.- The reaction between a metal and an organic halogen compound.- Thermochemical considerations.- Applications.- Alloy methods.- 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.- Boron and aluminium.- Addition of Group IVB hydrides to olefins.- Hydrosilation.- Formation of metal-carbon bonds by other insertion reactions.- Reactions of diazo compounds.- Aliphatic diazo compounds.- Reaction of aromatic diazonium salts with metal and metalloid halides or oxides in aqueous solution.- 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.- General characteristics.- (i) The alkali metals.- (ii) The second group metals.- (iii) The third group elements.- Structural aspects of the metal alkyls.- Preparative aspects.- The alkali metals: [A] Lithium.- (i) Lithium metal and halides.- (ii) Transmetalation.- (iii) Metal-halogen exchange.- (iv) Metal-hydrogen exchange (metalation).- (v) Analysis.- (vi) Some applications.- The alkali metals: [B] Sodium.- (i) Substitution compounds.- (ii) Addition compounds.- The Group IIA metals.- (i) Calcium, strontium and barium.- (ii) Magnesium.- (iii) Beryllium.- The Group IIB metals.- (i) Derivatives of the type RMX.- (ii) Dialkyls and diaryls.- The Group III elements.- (i) Boron.- (ii) Aluminium.- (iii) Gallium, indium and thallium.- Co-ordination chemistry.- (i) Boron.- (ii) Aluminium and the Group HIB elements.- (iii) Group II metals.- (iv) The alkali metals.- 4. Organometallic Compounds of Elements of Main Groups IV and V.- Group IVB elements.- Stabilities and reactivities.- Lower oxidation states-catenation.- Co-ordination number.- ?-Bonding to Group IVB elements.- Preparative aspects.- Some reactions.- Silicones.- The direct process for methylchlorosilanes.- The hydrolysis of methylchlorosilanes.- Silicone oils.- Silicone rubbers.- Silicone resins.- Miscellaneous silicone products.- Group VB elements.- Types of compound.- Donor-acceptor character and multiple bonding.- Catenation.- Onium salts.- Penta-alkyls and aryls.- Preparative aspects.- 5. Organometallic Compounds of the d-Block Transition Elements: Classification of Ligands and Theories of Bonding.- Classification of ligands.- The 18-electron rule.- Formal oxidation state.- The applicability of the 18-electron rule.- Basis of the 18-electron rule.- (i) The role of ?-bonding ligands.- (ii) Comparison of the 3d, 4d and 5d transition series.- (iii) Exceptions to the 18-electron rule.- Bonding in organometallic ?-complexes.- Energies of molecular orbitals.- A description of the bonding of ethylene to transition metals.- The rotation of ethylene about the ligand-metal bond.- The bonding of other unsaturated hydrocarbons to transition metals.- Comparison of conjugated and non-conjugated olefins as ligands.- 6. Preparation of Organo-Transition Metal Compounds.- General considerations.- Preparative routes.- From metal salt, reducing agent and ligand.- From metal and ligand.- From metal compounds and ligand, ligand displacement.- Substitution by organometallic derivatives of main group ele
