| Abstract: | The PM3(tm) semiempirical method has been used to optimize the structures for the reactants and transition states of the first and second ethylene insertion processes into zirconocene catalytic systems. The results obtained for these reactions are compared with calculations published in the literature performed at different ab-initio theoretical levels. The agreement between our calculations and those reported in the literature is satisfactory. Taking advantage of the reduced computational effort required in semiempirical calculations two additional processes related with the so-called comonomer effect were also studied: ethylene/1-hexene copolymerization, and chain termination reaction, both in the homopolymerization and in copolymerization of ethylene with 1-hexene comonomer. The calculated activation energies support some experimental findings such as the higher polymerization activities in the presence of comonomers and also the molecular weight reduction of the copolymers due to the more favorable β-elimination reactions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1157–1167, 1998 |
