Table of Contents:
  • Front Cover; Advances in Physical Organic Chemistry, Volume 23; Copyright Page; Contents; Contributors to Volume 23; Chapter 1. The Nucleophilicity of Metal Complexes Towards Organic Molecules; 1. The scope of the review; 2. Introduction to metal complexes as nucleophiles; 3. Types of metal-based nucleophiles; 4. The scale of nucleophilicity; 5. The influence of the solvent on the nucleophilicity; 6. Stereochemical changes at a saturated carbon centre; 7. Stereochemical changes at an unsaturated carbon centre; 8. Stereochemical changes at the metal; 9. The iodide catalysis effect.
  • 10. The reactions of binuclear complexes11. The reactivity of the carbon centre; 12. The reactions of a,?-dihalogenoalkanes; 13. Activation parameters; 14. Thermodynamics of reactions involving metal nucleophiles; 15. Activation of carbon-hydrogen bonds; 16. Applications; 17. Ad finem; Chapter 2. Isotope Effects on nmr Spectra of Equilibrating Systems; 1. Introduction; 2. Applications; Chapter 3. The Mechanisms of Reactions of ß-Lacta m Antibiotics; 1. Introduction; 2. Mode of action of ß-lactam antibiotics; 3. Is the antibiotic ß-lactam unusual?
  • 4. Alkaline hydrolysis and structure: chemical reactivity and relationships5. Acid hydrolysis; 6. Spontaneous hydrolysis; 7. Buffer catalysed hydrolysis; 8. Metal-ion catalysed hydrolysis; 9. Micelle catalysed hydrolysis of penicillins; 10. Cycloheptaamylose catalysed hydrolysis; 11. The aminolysis of ß-lactam antibiotics; 12. The stepwise mechanism for expulsion of C(3')-leaving groups in cephalosporins; 13. Reaction with alcohols and other oxygen nucleophiles; 14. Epimerisation of penicillin derivatives.
  • Chapter 4. Free Radical Chain Processes in Aliphatic Systems involving an Electron Transfer Process1. Introduction; 2. Free radical chain processes involving nucleophiles; 3. Free radical chain processes involving electron transfer between neutral substances; 4. Free radical chain reactions involving radical cations; 5. Concluding remarks; Author Index; Cumulative Index of Authors; Cumulative Index of Titles.