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Influence of solvation and dynamics on the mechanism and kinetics of nucleophilic aromatic substitution reactions in liquid ammonia

SLC Moors, B Brigou, Dietmar Hertsen UGent, B Pinter, P Geerlings, Veronique Van Speybroeck UGent, Saron Catak UGent and F De Proft (2016) JOURNAL OF ORGANIC CHEMISTRY. 81(4). p.1635-1644
abstract
The role of the solvent and the influence of dynamics On the kinetics and mechanism of the SNAr reaction of several halonitrobenzenes in liquid ammonia, using both static calculations and dynamic ab initio molecular dynamics simulations, are investigated. A combination of metadynamics and committor analysis methods reveals how this reaction can change from a concerted, one-step mechanism in gas phase to a stepwise pathway, involving a metastable Meisenheimer complex, in liquid ammonia. This clearly establishes, among others, the important role of the solvent and highlights the fact that accurately treating solvation is of crucial importance to correctly unravel the reaction mechanism. It is indeed shown that H-bond formation of the reacting NH3 with the solvent drastically reduces the barrier of NH3 addition. The halide elimination step, however, is greatly facilitated by proton transfer from the reacting NH3 to the solvent. Furthermore, the free energy surface strongly depends on the halide substituent and the number of electron-withdrawing nitro substituents.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
REACTIVITY, HYDROGEN, PATH, METALLABENZENES, SNAR, METADYNAMICS
journal title
JOURNAL OF ORGANIC CHEMISTRY
J. Org. Chem.
volume
81
issue
4
pages
1635 - 1644
publisher
AMER CHEMICAL SOC
place of publication
WASHINGTON
Web of Science type
Article
Web of Science id
000370768000031
JCR category
CHEMISTRY, ORGANIC
JCR impact factor
4.849 (2016)
JCR rank
8/59 (2016)
JCR quartile
1 (2016)
ISSN
0022-3263
DOI
10.1021/acs.joc.5b02794
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
7151282
handle
http://hdl.handle.net/1854/LU-7151282
date created
2016-03-17 08:48:32
date last changed
2017-01-02 09:56:23
@article{7151282,
  abstract     = {The role of the solvent and the influence of dynamics On the kinetics and mechanism of the SNAr reaction of several halonitrobenzenes in liquid ammonia, using both static calculations and dynamic ab initio molecular dynamics simulations, are investigated. A combination of metadynamics and committor analysis methods reveals how this reaction can change from a concerted, one-step mechanism in gas phase to a stepwise pathway, involving a metastable Meisenheimer complex, in liquid ammonia. This clearly establishes, among others, the important role of the solvent and highlights the fact that accurately treating solvation is of crucial importance to correctly unravel the reaction mechanism. It is indeed shown that H-bond formation of the reacting NH3 with the solvent drastically reduces the barrier of NH3 addition. The halide elimination step, however, is greatly facilitated by proton transfer from the reacting NH3 to the solvent. Furthermore, the free energy surface strongly depends on the halide substituent and the number of electron-withdrawing nitro substituents.},
  author       = {Moors, SLC and Brigou, B and Hertsen, Dietmar and Pinter, B and Geerlings, P and Van Speybroeck, Veronique and Catak, Saron and De Proft, F},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  keyword      = {REACTIVITY,HYDROGEN,PATH,METALLABENZENES,SNAR,METADYNAMICS},
  language     = {eng},
  number       = {4},
  pages        = {1635--1644},
  publisher    = {AMER CHEMICAL SOC},
  title        = {Influence of solvation and dynamics on the mechanism and kinetics of nucleophilic aromatic substitution reactions in liquid ammonia},
  url          = {http://dx.doi.org/10.1021/acs.joc.5b02794},
  volume       = {81},
  year         = {2016},
}

Chicago
Moors, SLC, B Brigou, Dietmar Hertsen, B Pinter, P Geerlings, Veronique Van Speybroeck, Saron Catak, and F De Proft. 2016. “Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia.” Journal of Organic Chemistry 81 (4): 1635–1644.
APA
Moors, SLC, Brigou, B., Hertsen, D., Pinter, B., Geerlings, P., Van Speybroeck, V., Catak, S., et al. (2016). Influence of solvation and dynamics on the mechanism and kinetics of nucleophilic aromatic substitution reactions in liquid ammonia. JOURNAL OF ORGANIC CHEMISTRY, 81(4), 1635–1644.
Vancouver
1.
Moors S, Brigou B, Hertsen D, Pinter B, Geerlings P, Van Speybroeck V, et al. Influence of solvation and dynamics on the mechanism and kinetics of nucleophilic aromatic substitution reactions in liquid ammonia. JOURNAL OF ORGANIC CHEMISTRY. WASHINGTON: AMER CHEMICAL SOC; 2016;81(4):1635–44.
MLA
Moors, SLC, B Brigou, Dietmar Hertsen, et al. “Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia.” JOURNAL OF ORGANIC CHEMISTRY 81.4 (2016): 1635–1644. Print.