Ab initio molecular dynamics simulations of organometallic reactivity

The energetics and reaction mechanism of prototypical organometallic reactions have been investigated by combining static and dynamic density functional calculations, based on the Car–Parrinello method. Such an approach allows us to dynamically sample the potential energy surface of the reactive system at finite temperature, providing useful insights into the reaction mechanism and evidencing the presence of reaction intermediates. Applications of this methodology are presented, ranging from the migratory insertions of carbon monoxide and alkyl-isocyanides into different metal–carbon bonds, to the SiH oxidative addition to Pt(PH3)2 and the acetylene to vinylidene isomerization in the coordination sphere of a transition metal center.