A dynamical density functional study of CO migration in the Reppe carbonylation

The migrative insertion of CO into the Ni-CH?CH2 bond has been investigated by both static and dynamic density functional methods. The stationary points of the potential surface for the migrative insertion of CO into the Ni-CH?CH2 bond have been characterized using Cl(CO)2Ni-CH?CH2 as a model compound. Such a reaction has been found exothermic by 16 kJ mol-1, with an energy barrier of 9 kJ mol-1. Dynamic simulations have also been performed on Cl(CO)2Ni-CH?CH2 and show that the migrative insertion begins from the cis isomer and occurs via a simultaneous detachment of the vinyl group from the metal and formation of the vinyl-carbonyl bond.