A dynamical density functional study of CO insertion into the metal–alkyl bond in Ti(Cp)2(CH3)2

The migratory insertion of CO into the titanium-methyl bond in Ti(Cp)(2)(CH3)(2) has been investigated by both static and dynamic density functional calculations. CO coordination prior to insertion has been analysed considering both "lateral" and "central" approaches, finding the two pathways kinetically equivalent. The relative stability of the O-outside and O-inside eta (2)-bound acyl complexes has been investigated, finding the O-outside isomer more stable by 4.0 kcal mol(-1), with an energy barrier for the conversion from the O-outside isomer of 9.6 kcal mol(-1). Dynamic simulations have also been performed on the Ti(Cp)(2)(CH3)(2)-CO adduct in order to study the detailed features of the CO migratory insertion and of the eta (1)--->eta (2)-acyl conversion, and show that migratory insertion takes place within 1 ps through detachment of the methyl group upon CO migration, leading to an O-inside eta (2)-acyl complex.