Ion‐Pair SN2 Substitution: Activation Strain Analyses of Counter‐Ion and Solvent Effects |
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| Authors: | Jalal Z A Laloo Dr Lydia Rhyman Prof?Dr Ponnadurai Ramasami Prof?Dr F Matthias Bickelhaupt Dr Abel de?Cózar |
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| Institution: | 1. Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, Mauritius;2. Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh, Saudi Arabia;3. Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, Amsterdam, The Netherlands;4. Institute of Molecules and Materials, Radboud University Nijmegen, Nijmegen, The Netherlands;5. Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco P. K. 1072, San Sebastián-Donostia, Spain;6. IKERBASQUE, Basque Foundation for Science, Bilbao, Spain |
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| Abstract: | The ion‐pair SN2 reactions of model systems MnFn?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 SN2 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. |
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| Keywords: | density functional calculations ion pairs reaction mechanisms solvent effects transition states |
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