TY - JOUR
T1 - Deciphering Front-Side Complex Formation in SN2 Reactions via Dynamics Mapping
AU - Szabó, István
AU - Olasz, Balázs
AU - Czakó, Gábor
PY - 2017/7/6
Y1 - 2017/7/6
N2 - Due to their importance in organic chemistry, the atomistic understanding of bimolecular nucleophilic substitution (SN2) reactions shows exponentially growing interest. In this publication, the effect of front-side complex (FSC) formation is uncovered via quasi-classical trajectory computations combined with a novel analysis method called trajectory orthogonal projection (TOP). For both F- + CH3Y [Y = Cl,I] reactions, the lifetime distributions of the F-⋯YCH3 front-side complex revealed weakly trapped nucleophiles (F-). However, only the F- + CH3I reaction features strongly trapped nucleophiles in the front-side region of the prereaction well. Interestingly, both back-side and front-side attack show propensity to long-lived FSC formation. Spatial distributions of the nucleophile demonstrate more prominent FSC formation in case of the F- + CH3I reaction compared to F- + CH3Cl. The presence of front-side intermediates and the broad spatial distribution in the back-side region may explain the indirect nature of the F- + CH3I reaction.
AB - Due to their importance in organic chemistry, the atomistic understanding of bimolecular nucleophilic substitution (SN2) reactions shows exponentially growing interest. In this publication, the effect of front-side complex (FSC) formation is uncovered via quasi-classical trajectory computations combined with a novel analysis method called trajectory orthogonal projection (TOP). For both F- + CH3Y [Y = Cl,I] reactions, the lifetime distributions of the F-⋯YCH3 front-side complex revealed weakly trapped nucleophiles (F-). However, only the F- + CH3I reaction features strongly trapped nucleophiles in the front-side region of the prereaction well. Interestingly, both back-side and front-side attack show propensity to long-lived FSC formation. Spatial distributions of the nucleophile demonstrate more prominent FSC formation in case of the F- + CH3I reaction compared to F- + CH3Cl. The presence of front-side intermediates and the broad spatial distribution in the back-side region may explain the indirect nature of the F- + CH3I reaction.
UR - http://www.scopus.com/inward/record.url?scp=85022078346&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.7b01253
DO - 10.1021/acs.jpclett.7b01253
M3 - Letter
AN - SCOPUS:85022078346
SN - 1948-7185
VL - 8
SP - 2917
EP - 2923
JO - Journal of physical chemistry letters
JF - Journal of physical chemistry letters
IS - 13
ER -