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Activation Strain Analyses of Counterion and Solvent Effects on the Ion‐Pair S N 2 Reaction of NH 2 − and CH 3 Cl
Author(s) -
Savoo Nandini,
Laloo Jalal Z. A.,
Rhyman Lydia,
Ramasami Ponnadurai,
Bickelhaupt F. Matthias,
Poater Jordi
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26104
Subject(s) - chemistry , solvation , counterion , nucleophile , reactivity (psychology) , tetrahydrofuran , solvent , polarizability , solvent effects , polarizable continuum model , ion , inorganic chemistry , medicinal chemistry , computational chemistry , organic chemistry , catalysis , molecule , medicine , alternative medicine , pathology
We have computationally studied the bimolecular nucleophilic substitution (S N 2) reactions of M n NH 2 (n−1) + CH 3 Cl (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 (S N 2‐b) versus frontside attack (S N 2‐f). The results were compared to the corresponding ion‐pair S N 2 reactions involving F − and OH − nucleophiles. Our analyses with an extended activation strain model of chemical reactivity uncover and explain various trends in S N 2 reactivity along the nucleophiles F − , OH − , and NH 2 − , including solvent and counterion effects. © 2019 Wiley Periodicals, Inc.