Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 126, Issue 9, Pages 1951-1961Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.1c09710
Keywords
-
Categories
Funding
- Swiss National Science Foundation [200020_188724]
- NCCR-MUST
- Swiss National Science Foundation (SNF) [200020_188724] Funding Source: Swiss National Science Foundation (SNF)
Ask authors/readers for more resources
In this study, the energetics and solvent distributions for the NH3+MeCl and Pyr+MeBr reactions were investigated using reactive molecular dynamics simulations. It was found that polar solvents and benzene exhibited strong to moderate catalytic effects, while the apolar and bulky cyclohexane showed weak interactions with the solute. The solvents' distributions changed considerably between the reactant and transition state, but showed comparatively little change between the transition state and product conformations of the solute.
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available