Ion-Pair SN 2 Substitution: Activation Strain Analyses of Counter-Ion and Solvent Effects
| Autor: | F. Matthias Bickelhaupt, Abel de Cózar, Ponnadurai Ramasami, Lydia Rhyman, Jalal Z. A. Laloo |
|---|---|
| Přispěvatelé: | Theoretical Chemistry, AIMMS |
| Rok vydání: | 2016 |
| Předmět: |
Substitution reaction
chemistry.chemical_classification Reaction mechanism 010405 organic chemistry Chemistry Organic Chemistry Solvation General Chemistry 010402 general chemistry 01 natural sciences Catalysis Transition state 0104 chemical sciences Crystallography Computational chemistry SN2 reaction Reactivity (chemistry) Solvent effects Counterion Theoretical Chemistry SDG 6 - Clean Water and Sanitation |
| Zdroj: | Chemistry : a European Journal, 22, 4431-4439 Laloo, I Z A, Rhyman, L, Ramasami, P, Bickelhaupt, F M & de Cozar, A 2016, ' Ion-Pair S N 2 Substitution: Activation Strain Analyses of Counter-Ion and Solvent Effects ', Chemistry: A European Journal, vol. 22, no. 13, pp. 4431-4439 . https://doi.org/10.1002/chem.201504456 Chemistry : a European Journal, 22, 13, pp. 4431-4439 Chemistry: A European Journal, 22(13), 4431-4439. Wiley-VCH Verlag |
| ISSN: | 0947-6539 |
| Popis: | The ion-pair SN 2 reactions of model systems MnF(n-1) +CH3Cl(M(+) =Li(+), Na(+), K(+), and MgCl(+); n=0, 1) have been quantum chemically explored by using DFT at the OLYP/6-31++G(d,p) level. The purpose of this study is threefold: 1) to elucidate how the counterion M(+) modifies ion-pair SN 2 reactivity relative to the parent reaction F(-) +CH3Cl; 2) to determine how this influences stereochemical competition between the backside and frontside attacks; and 3) to examine the effect of solvation on these ion-pair SN2 pathways. Trends in reactivity are analyzed and explained by using the activation strain model (ASM) of chemical reactivity. The ASM has been extended to treat reactivity in solution. These findings contribute to a more rational design of tailor-made substitution reactions. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|