Molecular modeling of the olefin metathesis by tungsten(0) carbene complexes

Density functional and second-order Moller-Plesset theory were used to mode l W(0) carbene mediated homogeneous metathesis reaction of propylene. The c alculations show that the rate determining step of the metathesis is the in itiation. After the initiation has been completed the rate determining step becomes dissociation of olefin-metallocarbene complex. The low stereoselec tivity of the olefin metathesis reaction is due to the close matching of ac tivation energies for cis and trans isomer formation and the fast cis-trans isomerization caused by the catalysts. The non-productive olefin metathesi s reaction always dominates the reaction mixture owing to its very low acti vation energy. The electronic structure of metal carbene olefin complexes c an be described as a combination of donor-acceptor interactions between HOM O of the olefin and LUMO of metal carbene located at carbene carbon on the one hand, and the Dewar, Chatt and Duncanson back donation scheme on the ot her. (C) 2001 Elsevier Science B.V. All rights reserved.