THE ELUCIDATION OF MECHANISMS IN HOMOGENEOUS CATALYSIS

After a reminder of the definition of common terms used in catalysis and reaction mechanisms, different chapters highlight the various approaches used for the elucidation of catalytic mechanisms, each with its own advantages and limitations. Kinetics investigations define the rate law and provide information on certain features of the reaction pathway between the resting state and the transition state of the rate-determining step. The use of isotope labels is useful in three ways: through the measurement of kinetic isotope effects, through the study of the incorporation into the products (regio-, stereochemical features), and through the incorporation into the incompletely converted reactants (reversibility). The investigation of isolated intermediates, if available, gives experimental structural information and thermodynamic/activation data on selected stoichiometric steps of the catalytic cycle. In situ spectroscopic investigations help determine the chemical nature of the resting state and other low-en...