Dynamic Effects Influencing Mechanisms and Selectivity in Metal-Mediated Organometallic Reactions

For organometallic reactions it has now become routine to calculate the molecular energy of stationary structures and stitch them together as a potential energy surface. This surface generally defines the reaction mechanism and is used to evaluate selectivity based on statistical transition-state theory. Recent computational studies have demonstrated that some organometallic reactions have nonstatistical behavior or dynamic effects where atomic motion plays a key role in the reaction mechanism and selectivity. The most tractable and straightforward method of identifying and demonstrating nonstatistical dynamic effects in organometallic reactions is the use of molecular dynamics simulations, which provides time-resolved atomic motion as reactions proceed. This tutorial provides examples of potential energy surfaces where molecular dynamics simulations are likely needed to understand and evaluate the reaction mechanism and selectivity. There is a concise overview of key concepts and issues when using and interpreting molecular dynamics simulations for organometallic reactions. Several key examples are highlighted to illustrate a variety of dynamic effects that have been identified in organometallic reactions.