TY - JOUR
T1 - Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair SN2 Reaction of NH2− and CH3Cl
AU - Savoo, Nandini
AU - Laloo, Jalal Z.A.
AU - Rhyman, Lydia
AU - Ramasami, Ponnadurai
AU - Bickelhaupt, F. Matthias
AU - Poater, Jordi
PY - 2020/2/5
Y1 - 2020/2/5
N2 - 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 (Formula presented.), including solvent and counterion effects.
AB - 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 (Formula presented.), including solvent and counterion effects.
KW - activation strain model
KW - amide
KW - DFT calculations
KW - ion-pair S2
KW - nucleophilic substitution
KW - solvent effects
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U2 - 10.1002/jcc.26104
DO - 10.1002/jcc.26104
M3 - Article
C2 - 31713259
AN - SCOPUS:85075207026
VL - 41
SP - 317
EP - 327
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 4
ER -