Determination of experimental kinetic isotope effects (KIE) is one of the most useful
tools for the exploration of reaction mechanisms in organometallic chemistry. The
approach has been further strengthened during the last decade with advances in modern
computational chemistry. This allows for the calculation of a theoretical KIE that
can often be compared directly to the experimental value. This combined experimental/theoretical
approach can be particularly useful in cases where the value of the experimental KIE
is not directly associated with one particular reaction step (e.g., in a catalytic
reaction). The approach is highlighted by using recent examples from both stoichiometric
and catalytic reactions, homogeneous and heterogeneous catalysis, and enzyme catalysis
to illustrate the expected accuracy and utility of this approach.
Keywords
kinetic isotope effect - competition experiments - density functional calculations
- catalysis
