Theoretical Study of Nucleophilic Identity Substitution Reactions at Nitrogen, Silicon and Phosphorus versus Carbon: Reaction Pathways, Energy Barrier, Inversion and Retention Mechanisms

• Published in: Journal of the Chinese Chemical Society (Taipei) 2013-03, Vol.60 (3), p.327-338
• Main Authors: Ding, Yan-Li, Mu, Ji-Rong, Gong, Li-Dong
• Format: Article
• Language: English
• Subjects: Ab initio method; Back-side attack; Front-side attack; Identity SN2(C); SN2(N); SN2(Si) and SN2(P) reactions
• ISSN: 0009-4536; 2192-6549
• DOI: 10.1002/jccs.201100750

Gas‐phase identity SN2(N), SN2(Si) and SN2(P) versus SN2(C) reactions with Cl− are investigated by the ab initio method. Front‐side attack identity SN2 reactions considered have all double‐well potential energy surfaces (PES), and back‐side attack identity SN2(C) and SN2(N) reactions have also double‐well PES, while back‐side attack identity SN2(Si) and SN2(P) have single‐well PES. In addition, the geometrical transformations, potential energy profiles of front‐side and back‐side attack identity SN2(N), SN2(Si) and SN2(P) versus SN2(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. Gas‐phase identity SN2(N), SN2(Si) and SN2(P) versus SN2(C) reactions with Cl− are investigated by the ab initio method. The geometrical transformations, potential energy profiles of front‐side and back‐side attack identity SN2(N), SN2(Si) and SN2(P) versus SN2(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.