Ion-Pair S(N)2 Reaction of OH- and CH3Cl: Activation Strain Analyses of Counterion and Solvent Effects
| Autor: | Lydia Rhyman, Ponnadurai Ramasami, Olatz Larrañaga, F. Matthias Bickelhaupt, Jalal Z. A. Laloo, Abel de Cózar |
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| Přispěvatelé: | Theoretical Chemistry, AIMMS |
| Rok vydání: | 2018 |
| Předmět: |
Implicit solvation
solvent effects 010402 general chemistry 01 natural sciences Biochemistry Polarizable continuum model Metal TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY Nucleophilic substitution SDG 7 - Affordable and Clean Energy Theoretical Chemistry ion pairs chemistry.chemical_classification 010405 organic chemistry Chemistry Organic Chemistry Solvation General Chemistry 0104 chemical sciences activation strain model visual_art density functional calculations visual_art.visual_art_medium Physical chemistry SN2 reaction Solvent effects Counterion nucleophilic substitution |
| Zdroj: | Chemistry, an Asian Journal, 13, 9, pp. 1138-1147 Chemistry, an Asian Journal, 13, 1138-1147 Laloo, J Z A, Rhyman, L, Larrañaga, O, Ramasami, P, Bickelhaupt, F M & de Cózar, A 2018, ' Ion-Pair S N 2 Reaction of OH − and CH 3 Cl : Activation Strain Analyses of Counterion and Solvent Effects ', Chemistry-An Asian Journal, vol. 13, no. 9, pp. 1138-1147 . https://doi.org/10.1002/asia.201800082 Chemistry-An Asian Journal, 13(9), 1138-1147. John Wiley and Sons Ltd |
| ISSN: | 1861-4728 |
| Popis: | We have theoretically studied the non-identity SN2 reactions of MnOH(n−1)+CH3Cl (M+=Li+, Na+, K+, and MgCl+; n=0, 1) in the gas phase and in THF solution at the OLYP/6-31++G(d,p) level using polarizable continuum model (PCM) implicit solvation. We want to explore and understand the effect of the metal counterion M+ and solvation on the reaction profile and the stereoselectivity of these processes. To this end, we have explored the potential energy surfaces of the backside (SN2-b) and frontside (SN2-f) pathways. To explain the computed trends, we have carried out analyses with an extended activation strain model (ASM) of chemical reactivity that includes the treatment of solvation effects. |
| Databáze: | OpenAIRE |
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