title: Ion-Pair SN 2 Substitution: Activation Strain Analyses of Counter-Ion and Solvent Effects.
abstract: 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.
authors.affiliation: Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius.
authors.forename: Jalal Z A
authors.identifier: http://orcid.org/0000-0003-2848-8805
authors.initials: JZ
authors.lastname: Laloo
authors.affiliation: Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius.
authors.forename: Lydia
authors.identifier: http://orcid.org/0000-0002-8624-8431
authors.initials: L
authors.lastname: Rhyman
authors.affiliation: Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius. ramchemi@intnet.mu.|Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, P.O. Box 2457, Riyadh, 11451, Saudi Arabia. ramchemi@intnet.mu.
authors.forename: Ponnadurai
authors.identifier: http://orcid.org/0000-0002-7272-3561
authors.initials: P
authors.lastname: Ramasami
authors.affiliation: Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands. f.m.bickelhaupt@vu.nl.|Institute of Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands. f.m.bickelhaupt@vu.nl.
authors.forename: F Matthias
authors.identifier: http://orcid.org/0000-0003-4655-7747
authors.initials: FM
authors.lastname: Bickelhaupt
authors.affiliation: Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands. a.de.cozar.ruano@vu.nl.|Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco P. K. 1072, 200880, San Sebastián-Donostia, Spain. a.de.cozar.ruano@vu.nl.|IKERBASQUE, Basque Foundation for Science, 48013, Bilbao, Spain. a.de.cozar.ruano@vu.nl.
authors.forename: Abel
authors.identifier: http://orcid.org/0000-0001-8430-4076
authors.initials: A
authors.lastname: de Cózar
keywords: density functional calculations; ion pairs; reaction mechanisms; solvent effects; transition states