title: A detailed analysis of the mechanism of a carbocationic triple shift rearrangement.
abstract: The mechanism of a carbocationic triple shift rearrangement is analyzed within the conceptual framework of the reaction force. All the systems were characterized computationally using DFT through B3LYP/6-31+G(d,p) methodology. A complete description of the electronic activity taking place during the reaction emerged through the use of the reaction electronic flux that, together with an NBO Wiberg bond order, produces a detailed picture of the reaction mechanism in terms of chemical events that drive the reaction during the different stages of the process. It is found that a carbocation triple shift occurs asynchronously although in a concerted way.
authors.affiliation: Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile. atola@pucd.cl.
authors.forename: Daniela E
authors.initials: DE
authors.lastname: Ortega
authors.forename: Soledad
authors.initials: S
authors.lastname: Gutiérrez-Oliva
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
authors.forename: Alejandro
authors.initials: A
authors.lastname: Toro-Labbé
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002412:Cations; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D002412:Cations; D002244:Carbon