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Moors SL, Brigou B, Hertsen D, et al. Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia. J Org Chem. 2016;81(4):1635-44doi: 10.1021/acs.joc.5b02794.
Moors, S. L., Brigou, B., Hertsen, D., Pinter, B., Geerlings, P., Van Speybroeck, V., Catak, S., & De Proft, F. (2016). Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia. The Journal of organic chemistry, 81(4), 1635-44. https://doi.org/10.1021/acs.joc.5b02794
Moors, Samuel L C, et al. "Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia." The Journal of organic chemistry vol. 81,4 (2016): 1635-44. doi: https://doi.org/10.1021/acs.joc.5b02794
Moors SL, Brigou B, Hertsen D, Pinter B, Geerlings P, Van Speybroeck V, Catak S, De Proft F. Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia. J Org Chem. 2016 Feb 19;81(4):1635-44. doi: 10.1021/acs.joc.5b02794. Epub 2016 Feb 05. PMID: 26800020.
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J Org Chem. 2016 Feb 19;81(4):1635-44. doi: 10.1021/acs.joc.5b02794. Epub 2016 Feb 05.

Influence of Solvation and Dynamics on the Mechanism and Kinetics of Nucleophilic Aromatic Substitution Reactions in Liquid Ammonia.

The Journal of organic chemistry

Samuel L C Moors, Ben Brigou, Dietmar Hertsen, Balazs Pinter, Paul Geerlings, Veronique Van Speybroeck, Saron Catak, Frank De Proft

Affiliations

  1. Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB) , Pleinlaan 2, 1050 Elsene, Brussels, Belgium.
  2. Center for Molecular Modeling (CMM), Ghent University , Technologiepark 903, 9052 Zwijnaarde, Belgium.
  3. Department of Chemistry, Bogazici University , Bebek 34342, Istanbul, Turkey.

PMID: 26800020 DOI: 10.1021/acs.joc.5b02794

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.

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