Energetics of Organometallic Species

An overview of modern organometallic thermochemistry, made by some of the most active scientists in the area, is offered in this book. The contents correspond to the seventeen lectures delivered at the NATO ASI Energetics of Organometallic Species (Curia, Portugal, September 1991), plus three other invited contributions from participants of that summer school. These papers reflect a variety of research interests, and discuss results obtained with several techniques. It is therefore considered appropriate to add a few preliminary words, attempting to bring some unity out of that diversity. In the first three chapters, results obtained by classical calorimetric methods are described. Modern organometallic thermochemistry started in Manchester, with Henry Skinner, and his pioneering work is briefly surveyed in the first chapter. The historical perspective is followed by a discussion of a very actual issue: the trends of stepwise bond dissociation enthalpies. Geoff Pilcher, another Manchester thermochemist, makes, in chapter 2, a comprehensive and authoritative survey of problems found in the most classical of thermochemical techniques - combustion calorimetr- applied to organometallic compounds. Finally, results from another classical technique, reaction-solution calorimetry, are reviewed in the third chapter, by Tobin Marks and coworkers. More than anybody else, Tobin Marks has used thermochemical values to define synthetic strategies for organometallic compounds, thus indicating an application of thermochemical data of which too little use has been made so far.

Texte du rabat

Why has the energetics of organometallic species become an area of recognized importance? What methods are available to obtain information on reaction enthalpies and bond `strengths'? What other methods are likely to be used in the future? Is the present thermochemical data bank satisfactory for our needs? How accurately can we estimate the energetics of organometallic reactions? Can theory offer reliable help? Which are the main problems to be tackled by the experimentalist? br/ These are some of the questions addressed in the present book, which contains contributions by most of the leading groups in the area of organometallic thermochemistry. br/

Contenu

1. Historical Perspective of Organometallic Thermochemistry.- 2. Combustion Calorimetry of Organometallic Compounds.- 3. Organo-f-Element Thermochemistry. Implications for Reactivity and Bonding from Metal-Ligand Bonding Energetics.- 4. The Role of Bond Energies in Hydrocarbon Activation by Transition Metal Centers.- 5. Rh-C Bond Dissociation Enthalpies for Organometallic Derivatives of Rhodium Porphyrins.- 6. Solution Thermochemistry of Organometallic Compounds Using Photoacoustic Calorimetry: Enthalpies of Ligand Exchange, Metal-Ligand Bonds, and Metal-Solvent Interactions.- 7. Electrochemistry of Some Organic and Organometallic Radicals and their Application in Thermochemical Cycles.- 8. Derivative Cyclic Voltammetry: Applications in the Investigation of the Energetics of Organometallic Electrode Reactions.- 9. The Use of Calorimetric and Sublimation Techniques to Study Bond Properties in Organometallic Compounds.- 10. Estimating Enthalpies of Sublimation of Hydrocarbons.- 11. Derivation of Thermodynamic Quantities from Kinetic Measurements in Gas Phase Silane Chemistry.- 12. Bond Enthalpy Transferability - is it Achievable?.- 13. Estimates of Thermochemical Data for Organometallic Compounds.- 14. Bonding and Solvation Energetics for Organometallic Gas-Phase Molecules and Ions: Experimental Approaches and Thermodynamic Insights.- 15. Gas-Phase Acidities of Transition-Metal Carbonyl and Trifluorophosphine Hydrides.- 16. Bond Strengths in Transition Metal Carbonyl Anions.- 17. Fundamental Gas Phase Studies of the Mechanism and Thermochemistry of Organometallic Reactions.- 18. Guided Ion Beam Studies of the Energetics of Organometallic Species.- 19. A Guide to Density Functional Theory and Its Practical Applications to the Energetics of Organometallic Species.- 20. Theoretical Models for Organometallic Reactions.- List of Posters and Contributed Oral Presentations.- List of Participants.