Equilibrium and non-equilibrium solvent effects in electrophilic halogenation of ethylenic compounds

Autor:	Jean-Louis Rivail, J. Garapon, Manuel F. Ruiz-López, Daniel Rinaldi, Xavier Assfeld
Rok vydání:	1996
Předmět:	chemistry.chemical_classification Alkene Solvation Halogenation Condensed Matter Physics Biochemistry Transition state Reaction coordinate Solvation shell chemistry Computational chemistry SN2 reaction Physics::Chemical Physics Physical and Theoretical Chemistry Solvent effects
Zdroj:	Journal of Molecular Structure: THEOCHEM. 371:107-116
ISSN:	0166-1280
DOI:	10.1016/s0166-1280(96)04530-7
Popis:	Alkene halogenation belongs to a class of reactions known to be extremely sensitive to the environmental effect. In this article we discuss different aspects of the problem through ab initio calculations. Discrete and continuum models for the solvent are employed to analyse equilibrium and non-equilibrium solvation effects on the reaction of ethylene with molecular bromine. It is shown that there are two mechanisms that lead to transition states of different symmetry. One mechanism is found in gas phase and non-polar solvents. The second one, that leads to the typical C2v transition state, holds in medium polar to very polar media. In water, the solvent molecules participate actively to the reaction coordinate. In this solvent, non-equilibrium solvation effects are shown to be substantial and larger that those previously reported for the SN2 reaction.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::40325e5119908df924e9dfef34cb1853 https://doi.org/10.1016/s0166-1280(96)04530-7 Zobrazit plný text záznamu Full Text from ScienceDirect