Nonempirical calculations on potential surfaces for gas-phase SN2 nucleophilic substitution reactions

1986 ◽  
Vol 22 (3) ◽  
pp. 253-260
Author(s):  
V. M. Ryaboi
Keyword(s):  
Nucleophilic Substitution ◽  
Gas Phase ◽  
Substitution Reactions ◽  
Potential Surfaces ◽  
Nucleophilic Substitution Reactions ◽  
Nonempirical Calculations

STUDIES ON NUCLEOPHILIC SUBSTITUTION REACTIONS AT CARBON (SN2(C)) AND SILICON (SN2(Si)) IN TERMS OF AB INITIO, POTENTIAL, ACTING ON AN ELECTRON IN A MOLECULE AND MOLECULAR FACE THEORY

2009 ◽  
Vol 08 (supp01) ◽  
pp. 983-1001 ◽  
Author(s):  
YAN-LI DING ◽  
LI-DONG GONG ◽  
DONG-XIA ZHAO ◽  
MING-BO ZHANG ◽  
ZHONG-ZHI YANG
Keyword(s):  
Ab Initio ◽  
Nucleophilic Substitution ◽  
Gas Phase ◽  
Chemical Bond ◽  
Energy Transition ◽  
High Energy ◽  
Ab Initio Method ◽  
Substitution Reactions ◽  
Nucleophilic Substitution Reactions ◽  
High Energy Transition

The gas-phase identity bimolecular nucleophilic substitution reactions, Cl- + CH3 Cl → ClCH3 + Cl- and Cl- + SiH3Cl → ClSiH3 + Cl- , are investigated in terms of the ab initio method, potential acting on an electron in a molecule (PAEM) and molecular face (MF) theory. The computations have been performed at the CCSD(T)/aug-cc-pVTZ//MP2/6-311+G(3df,3pd) and CISD/aug-cc-pVDZ level. Based on the ab initio calculation, according to the PAEM theory, the strength of a chemical bond during forming or rupturing may be characterized by the D pb , which is a new physical quantity relating to the barrier height of the PAEM along a chemical bond. According to the MF theory, the interesting pictures of electron transfer and interpolarization effect between the reactants are clearly demonstrated to provide visualized spatial changing features of the MF for the title reactions along the IRC routes. The reason why [ Cl⋯CH3⋯Cl]- is a high-energy transition state is also analyzed in comparison with the stable low-energy intermediate [ Cl⋯SiH3⋯Cl]- .

Gas-Phase Identity Nucleophilic Substitution Reactions of Cyclopropenyl Halides

2002 ◽  
Vol 67 (6) ◽  
pp. 1953-1960 ◽  
Author(s):  
Chang Kon Kim ◽  
Hong Guang Li ◽  
Bon-Su Lee ◽  
Chan Kyung Kim ◽  
Hai Whang Lee ◽  
...  
Keyword(s):  
Nucleophilic Substitution ◽  
Gas Phase ◽  
Substitution Reactions ◽  
Nucleophilic Substitution Reactions
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