Abstract

The mechanism of the reaction of lithium and magnesium carbenoids with ethylene to give cyclopropane has been explained in detail in all the steps at the G4 level of theory. We explored the lithium and magnesium interaction toward pi(C=C) and sigma(C-C) bonds in the reactants and the products. We have also investigated the reaction path by means of the force profile formalism in order to highlight the electronic and the structural rearrangements along the potential energy surface of the cyclopropanation. The results indicate that all of the reactions are stepwise, exoenergetic, with low barriers. All our findings were confirmed by dynamic simulations for chlorometal carbenoids. Furthermore, from the intrinsic reaction coordinate procedure, we were able to find out the intermediates that can take place when the reaction is descending from the transition state to the products or reactants. The reaction force analysis at B3LYP/6-311G(d,p) indicates that the energy barriers are mostly due to structural rearrangements which are produced by the approach of the carbenoid to ethylene. Quantum theory of atoms in molecules and electron localization function analyses indicate that products, reactants, and intermediates form complexes stabilized by attractive forces between Li/Mg and single/double bonds.