1. Chemical kinetics and reaction mechanisms.- 1.1. Introduction.- 1.2. Chemical reactions and energy changes.- 1.3. Collision theory.- 1.3.1. Calculation of rate constants.- 1.3.2. Arrhenius equation.- 1.4. Transition state theory.- 1.5. Steric effects and reactivity of strictly oriented molecules.- 1.5.1. Molecular beams studies.- 1.5.2. Symmetric top molecules.- 1.6. Reaction energy profiles and the reaction coordinate.- 1.7. Bimolecular and unimolecular nucleophilic substitutions (SN2 and SN1 substitutions).- 1.8. Novel views on the mechanism of bimolecular substitutions in the gas phase.- 1.9. Classification of reaction mechanisms in inorganic chemistry involving metal complexes (D, A, Id and Ia mechanisms).- 1.9.1. The collision theory in solutions.- 1.9.2. Primary kinetic salt effect.- 1.9.3. IUPAC recommendations for the representation of reaction mechanisms.- 1.9.4. Nomenclature of coordination compounds.- 1.10. Direct observation of the activated complex.- 1.10.1 Spectroscopy in the transition state region.- 1.11. The influence of the solvent on the reaction rates and mechanisms.- 1.11.1. Influence of solvent polarity on the rates of chemical reactions.- 184.108.40.206. Entropy change in charge separation.- 220.127.116.11. The effect of solvents on reaction rates.- 18.104.22.168. The ionizing power of solvents.- 22.214.171.124. Ionic strength of the medium and the reaction rate.- 126.96.36.199. Linear free energy relationships.- 188.8.131.52. Solvent nucleophilicity and definition of the nucleophilic constant N.- 184.108.40.206. Solvent coordinating property and electron-donor ability.- 220.127.116.11. Drastic acceleration of the oxidation of hexacyanoferrate(II) in solvents, strong electron donors.- 18.104.22.168. The dissociative type reaction may not depend on solvent polarity.- 1.12. Steady-state approximation and its application to replacement reactions.- 1.13. Reactions of ion pairs.- 1.14. Primary and secondary kinetic isotope effects.- 1.14.1. Primary kinetic isotope effects.- 22.214.171.124. Primary kinetic isotope effect of sulfur-34.- 126.96.36.199. Isotope effects and the mechanism of enzymatic catalysis.- 1.14.2. Secondary kinetic isotope effects.- 188.8.131.52. Secondary ß-deuterium kinetic isotope effect.- 184.108.40.206. Secondary ?-deuterium kinetic isotope effect.- 1.15. Influence of tunneling on the primary and secondary kinetic isotope effects.- 1.15.1. Extremely high kinetic isotope effects and tunneling.- 1.15.2. Secondary ?-deuterium kinetic isotope effect and tunneling.- 220.127.116.11. Reaction branching and extreme kinetic isotope effects.- References.- 2. Substitution reactions on metal complexes.- 2.1. Introduction.- 2.2. Reactions of organometallic complexes with halogenes (SE2 mechanism).- 2.3. Labile and inert complexes.- 2.4. Crystal-field theory.- 2.4.1. Splitting of d orbitals in the octahedral crystal field.- 2.4.2. Crystal-field stabilization energies of d orbitals for various geometric configurations, and substitution rates.- 2.4.3. Influence of crystal field stabilization energies on the rates and mechanism of octahedral substitutions.- 2.5. Ligand field and electron transitions.- 2.6. Substitution reactions on octahedral complexes.- 2.6.1. Rates of water exchange in octahedral aqua complexes.- 2.6.2. Pressure dependence of the reaction rate constant; volume of activation.- 2.6.3. Substitution of coordinated water of octahedral complexes with anions ("anations").- 2.6.4. Aquation and acid catalysis.- 2.6.5. Base catalysis.- 2.6.6. Stereochemistry of octahedral substitutions.- 2.6.7. Attacks of reactants on ligands (not on metal).- 2.6.8. Linkage isomerism.- 2.7. Nucleophilicity in inorganic chemistry.- 2.7.1. npt Scale.- 2.7.2. The scale of Swain and Scott.- 2.7.3. Edwards' scale.- 2.7.4. The theory of "hard" and "soft" acids and bases.- 2.8. Substitutions on square-planar complexes.- 2.8.1. The mechanism of ligand replacements.- 2.8.2. Trans effect.- 2.8.3. Cis effect.- 2.8.4. Leaving group effects.- 2.8.5. Effect of the central metal ion.- 2.9. Sub
The serious study of the reaction mechanisms of transition metal com plexes began some five decades ago. Work was initiated in the United States and Great Britain; the pioneers ofthat era were, inalphabetical order, F. Basolo, R. E. Connick, 1. O. Edwards, C. S. Garner, G. P.Haight, W. C. E. Higgision, E.1. King, R. G. Pearson, H. Taube, M.1. Tobe, and R. G. Wilkins.A larger community of research scientists then entered the field, many of them stu dents ofthose just mentioned. Interest spread elsewhere as well, principally to Asia, Canada, and Europe. Before long, the results ofindividual studies were being consolidated into models, many of which traced their origins to the better-established field of mechanistic organic chemistry. For a time this sufficed, but major revisions and new assignments of mechanism became necessary for both ligand sub stitution and oxidation-reduction reactions. Mechanistic inorganic chemistry thus took on a shape of its own. This process has brought us to the present time. Interests have expanded both to include new and more complex species (e.g., metalloproteins) and a wealth of new experimental techniques that have developed mechanisms in ever-finer detail. This is the story the author tells, and in so doing he weaves in the identities of the investigators with the story he has to tell. This makes an enjoyable as well as informative reading.
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