Solvent Effects on the Menshutkin Reaction

Turan, Haydar Taylan and Brickel, Sebastian and Meuwly, Markus. (2022) Solvent Effects on the Menshutkin Reaction. Journal of Physical Chemistry B, 126 (9). pp. 1951-1961.

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Official URL: https://edoc.unibas.ch/93154/

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The Menshutkin reaction is a methyl transfer reaction relevant in fields ranging from biochemistry to chemical synthesis. In the present work, the energetics and solvent distributions for NH3+MeCl and Pyr+MeBr reactions were investigated in explicit solvent (water, methanol, acetonitrile, benzene, cyclohexane) by means of reactive molecular dynamics simulations. For polar solvents (water, methanol, and acetonitrile) and benzene, strong to moderate catalytic effects for both reactions were found, whereas apolar and bulky cyclohexane interacts weakly with the solute and does not show pronounced barrier reduction. The calculated barrier heights for the Pyr+MeBr reaction in acetonitrile and cyclohexane are 23.2 and 28.1 kcal/mol compared with experimentally measured barriers of 22.5 and 27.6 kcal/mol, respectively. The solvent distributions change considerably between reactant and TS but comparatively little between TS and product conformations of the solute. As the system approaches the transition state, correlated solvent motions occur which destabilize the solvent–solvent interactions. This is required for the system to surmount the barrier. Finally, it is found that the average solvent–solvent interaction energies in the reactant, TS, and product state geometries are correlated with changes in the solvent structure around the solute.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Meuwly, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:16 Feb 2023 10:21
Deposited On:16 Feb 2023 10:01

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