Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair SN2 Reaction of and CH3Cl |
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| Authors: | Nandini Savoo Jalal Z A Laloo Lydia Rhyman Ponnadurai Ramasami F Matthias Bickelhaupt Jordi Poater |
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| Institution: | 1. Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837 Mauritius;2. Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, NL-1081 HV Amsterdam, The Netherlands;3. Departament de Química Inorgànica i Orgànica & IQTCUB, Universitat de Barcelona, 08028 Barcelona, Spain |
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| Abstract: | We have computationally studied the bimolecular nucleophilic substitution (SN2) reactions of MnNH2(n−1) + CH3Cl (M+ = Li+, Na+, K+, and MgCl+; n = 0, 1) in the gas phase and in tetrahydrofuran solution at OLYP/6-31++G(d,p) using polarizable continuum model implicit solvation. We wish to explore and understand the effect of the metal counterion M+ and of solvation on the reaction profile and the stereochemical preference, that is, backside (SN2-b) versus frontside attack (SN2-f). The results were compared to the corresponding ion-pair SN2 reactions involving F− and OH− nucleophiles. Our analyses with an extended activation strain model of chemical reactivity uncover and explain various trends in SN2 reactivity along the nucleophiles F−, OH−, and  , including solvent and counterion effects. © 2019 Wiley Periodicals, Inc. |
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| Keywords: | activation strain model amide DFT calculations ion-pair SN2 nucleophilic substitution solvent effects |
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