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Frontside versus Backside S N 2 Substitution at Group 14 Atoms: Origin of Reaction Barriers and Reasons for Their Absence
Author(s) -
Bento A. Patrícia,
Bickelhaupt F. Matthias
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200800065
Subject(s) - pseudorotation , chemistry , nucleophilic substitution , nucleophile , leaving group , density functional theory , group (periodic table) , transition state , turnstile , crystallography , substitution reaction , reaction mechanism , computational chemistry , atom (system on chip) , stereochemistry , medicinal chemistry , molecule , catalysis , organic chemistry , linguistics , philosophy , computer science , embedded system
We have theoretically studied the gas‐phase nucleophilic substitution at group‐14 atoms (S N 2@A) in the model reactions of Cl − +AH 3 Cl (A=C, Si, Ge, Sn, and Pb) using relativistic density functional theory (DFT) at ZORA‐OLYP/TZ2P. Firstly, we wish to explore and understand how the reaction coordinate ζ, and potential energy surfaces (PES) along ζ, vary as the center of nucleophilic attack changes from carbon to the heavier group‐14 atoms. Secondly, a comparison between the more common backside reaction (S N 2‐b) and the frontside pathway (S N 2‐f) is performed. The S N 2‐b reaction is found to have a central barrier for A=C, but none for the other group‐14 atoms, A=Si–Pb. Relativistic effects destabilize reactant complexes and transition species by up to 10 kcal mol −1 (for S N 2‐f@Pb), but they do not change relative heights of barriers. We also address the nature of the transformation in the frontside S N 2‐f reactions in terms of turnstile rotation versus Berry‐pseudorotation mechanism.