The reaction mechanism in aromatic nucleophilic substitution reactions is discussed using kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of biothiols toward atrazine (ATZ) in aqueous media. The proposed reaction mechanism discloses a non-catalyzed pathway and the presence of a deprotonated (thiolate) nucleophile in water suggests that the reaction mechanism is borderline between a stepwise route and a concerted process. The full analysis of the potential energy surface reinforces the addition/elimination mechanism. Despite numerous attempts to locate transition structures associated with the leaving group departure, they were unsuccessful, presumably because this step is extremely fast.
%0 Journal Article
%1 RN377
%A Calfuman, K.
%A Gallardo-Fuentes, S.
%A Contreras, R.
%A Tapia, R.A.
%A Campodonico, P.R.
%D 2017
%J New Journal of Chemistry
%K acetonitrile, aromatic-substitution dqcauchile ions, path protein, reactions, rings, sites,
%N 21
%P 12671-12677
%R 10.1039/c7nj02708g
%T Mechanism for the Snar Reaction of Atrazine with Endogenous Thiols: Experimental and Theoretical Study
%U /brokenurl#<Go to ISI>://WOS:000413526200036
%V 41
%X The reaction mechanism in aromatic nucleophilic substitution reactions is discussed using kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of biothiols toward atrazine (ATZ) in aqueous media. The proposed reaction mechanism discloses a non-catalyzed pathway and the presence of a deprotonated (thiolate) nucleophile in water suggests that the reaction mechanism is borderline between a stepwise route and a concerted process. The full analysis of the potential energy surface reinforces the addition/elimination mechanism. Despite numerous attempts to locate transition structures associated with the leaving group departure, they were unsuccessful, presumably because this step is extremely fast.
@article{RN377,
abstract = {The reaction mechanism in aromatic nucleophilic substitution reactions is discussed using kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of biothiols toward atrazine (ATZ) in aqueous media. The proposed reaction mechanism discloses a non-catalyzed pathway and the presence of a deprotonated (thiolate) nucleophile in water suggests that the reaction mechanism is borderline between a stepwise route and a concerted process. The full analysis of the potential energy surface reinforces the addition/elimination mechanism. Despite numerous attempts to locate transition structures associated with the leaving group departure, they were unsuccessful, presumably because this step is extremely fast.},
added-at = {2019-12-04T03:57:35.000+0100},
author = {Calfuman, K. and Gallardo-Fuentes, S. and Contreras, R. and Tapia, R.A. and Campodonico, P.R.},
biburl = {https://www.bibsonomy.org/bibtex/27e142f4850abef7196f0f23966336cb0/dqcauchile},
doi = {10.1039/c7nj02708g},
interhash = {4d5999fc52ea5e8485bcddc603ed78c5},
intrahash = {7e142f4850abef7196f0f23966336cb0},
issn = {1144-0546},
journal = {New Journal of Chemistry},
keywords = {acetonitrile, aromatic-substitution dqcauchile ions, path protein, reactions, rings, sites,},
number = 21,
pages = {12671-12677},
timestamp = {2019-12-04T03:58:17.000+0100},
title = {Mechanism for the Snar Reaction of Atrazine with Endogenous Thiols: Experimental and Theoretical Study},
type = {Journal Article},
url = {/brokenurl#<Go to ISI>://WOS:000413526200036},
volume = 41,
year = 2017
}