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Theoretical Study of Nucleophilic Identity Substitution Reactions at Nitrogen, Silicon and Phosphorus versus Carbon: Reaction Pathways, Energy Barrier, Inversion and Retention Mechanisms
Author(s) -
Ding YanLi,
Mu JiRong,
Gong LiDong
Publication year - 2013
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201100750
Subject(s) - chemistry , identity (music) , kinetic energy , nucleophile , inversion (geology) , ab initio , side chain , silicon , nitrogen , computational chemistry , stereochemistry , organic chemistry , paleontology , physics , polymer , quantum mechanics , structural basin , acoustics , biology , catalysis
Abstract Gas‐phase identity S N 2(N), S N 2(Si) and S N 2(P) versus S N 2(C) reactions with Cl − are investigated by the ab initio method. Front‐side attack identity S N 2 reactions considered have all double‐well potential energy surfaces (PES), and back‐side attack identity S N 2(C) and S N 2(N) reactions have also double‐well PES, while back‐side attack identity S N 2(Si) and S N 2(P) have single‐well PES. In addition, the geometrical transformations, potential energy profiles of front‐side and back‐side attack identity S N 2(N), S N 2(Si) and S N 2(P) versus S N 2(C) reactions based on the IRC calculations are described, the differences between them for the front‐side or back‐side attack reactions have been demonstrated.