Revisiting the Dielectric Constant Effect on the Nucleophile and Leaving Group of Prototypical Backside SN2 Reactions: A Reaction Force and Atomic Contribution Analysis
| Autor: | Ronald Gonzalez, Laura Pedraza-González, Andrés Reyes, Johan F. Galindo |
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| Rok vydání: | 2016 |
| Předmět: |
010304 chemical physics
Chemistry Leaving group Dielectric 010402 general chemistry Photochemistry 01 natural sciences 0104 chemical sciences Solvent Nucleophile Polarizability 0103 physical sciences Nucleophilic substitution SN2 reaction Physical chemistry Physical and Theoretical Chemistry Solvent effects |
| Zdroj: | The Journal of Physical Chemistry A. 120:8360-8368 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.6b06517 |
| Popis: | The solvent effect on the nucleophile and leaving group atoms of the prototypical F– + CH3Cl → CH3F + Cl– backside bimolecular nucleophilic substitution reaction (SN2) is analyzed employing the reaction force and the atomic contributions methods on the intrinsic reaction coordinate (IRC). Solvent effects were accounted for using the polarizable continuum solvent model. Calculations were performed employing 11 dielectric constants, e, ranging from 1.0 to 78.5, to cover a wide spectrum of solvents. The reaction force data reveal that the solvent mainly influences the region of the IRC preceding the energy barrier, where the structural rearrangement to reach the transition state occurs. A detailed analysis of the atomic role in the reaction as a function of e reveals that the nucleophile and the carbon atom are the ones that contribute the most to the energy barrier. In addition, we investigated the effect of the choice of nucleophile and leaving group on the ΔE0 and ΔE‡ of Y– + CH3X → YCH3 + X– (X, Y = F, C... |
| Databáze: | OpenAIRE |
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