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

ZALAZAR, M. FERNANDA; PERUCHENA, NÉLIDA MARIA

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

JOHN WILEY & SONS LTD

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

0894-3230

In this work, we applied the theory of Atoms in Molecules to the study of carbocationic transition states involved in two different reaction mechanisms, using the proposed mechanism of ethylene dimerization over Brønsted acid site of zeolite catalyst as a study case. We report the main results of the analysis of the Laplacian of electron density distribution and Bader´s atomic charges to increase our understanding of stereoelectronic aspects of these chemical reactions. At B3LYP/6-31++G(d,p)//B3LYP/6-31G(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, their interaction with the catalyst surface, and its stability. The stabilization and formation of these transition states depend on the availability of electrons in the environment. Such availability plays a key role to stabilize the positive charge on the carbocationic center and, thus, to stabilize the formed carbocation. The analysis of envelopes of Laplacian could be used to study different organic and inorganic chemical reactions and provide new insights to increase our understanding of these chemical reactions.