Can molecular quantum descriptors predict the butene selectivity in nickel(II) catalyzed ethylene dimerization? A QSPR study

Abstract

AbstractIn this article, we assess the ability of common molecular descriptors issued from quantum chemistry calculations (geometrical parameters, atomic charges, isodesmic energies, polarizabilities, and descriptors from conceptual DFT) to predict the butene selectivity in the mixed (P,N)‐nickel(II) catalyzed ethylene dimerization process. To this aim, 29 active species are considered, characterized by different substitution patterns on the nitrogen and phosphorus atoms. For each of them, the Gibbs energy difference between the transition states for the third ethylene insertion and for the butene elimination is computed to characterize the selectivity. Our results show that, in contrast to previously reported catalysts, the studied descriptors did not show any significant correlations with the property to predict and their integration in a multivariate analysis was not more efficient for the considered catalytic systems. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010