Reaction Types and Mechanisms

The reaction types discussed in this chapter are proton transfer, substitution, oxidation–reduction, oxidative-addition, and isomerization. The development of a theoretical rate law and the effects of temperature and pressure on the rate constant are outlined. For proton transfer reactions, typical rate constants and the Grotthuss mechanism are described. For substitution reactions, the nucleophilic and electrophilic classification is discussed, along with the D, Id, Ia, and I classification system. For oxidation–reduction reactions, topics such as electron versus atom transfer, inner sphere and outer sphere electron transfer, and Marcus theory are covered. Possible oxidative-addition mechanisms are described, with examples involving the metals in Groups 8, 9, and 10. Dissociative and intramolecular mechanisms are described for linkage isomerization, geometrical isomerization, and racemization. The coverage of these topics includes references published through to mid-2021.