Laplacian of the electron density: a hole-lump interaction as a tool to study stereoelectronic control of chemical reactions.

ZALAZAR, M. F.; PERUCHENA, N. M.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

JOHN WILEY & SONS LTD

Lugar: Londres; Año: 2014 vol. 27 p. 327 - 335

0894-3230

In this work Atoms in Molecules theory was applied for the study of carbocationic transition states involved in two different reaction mechanisms. The reaction mechanisms proposed in ethylene dimerization reaction over Brønsted acid site of zeolite catalyst have been chosen as a study case. We report the main results of the analysis of the Laplacian of electron density distribution, in conjunction with the Bader´s atomic charges, in order to gain a deeper understanding of stereoelectronic aspects of these chemical reactions. At B3LYP/6?31++G(d,p)//B3LYP/6?3G(d,p) level, our results show that the envelopes of Laplacian distribution provide valuable information about the relative orientation of the species involved in the reaction, its interaction with the catalyst surface and its stability. The stabilization and formation of these transition states depends on the availability of electrons in the environment which plays a key role in stabilizing the positive charge on the carbocationic center and thus the carbocation formed. Summing up, the study of envelopes of Laplacian could be used for the study of different organic and inorganic chemical reactions providing new insights for a deeper understanding of these chemical reactions.