Density functional theory study on the reactions of X− with CH3SY (X,Y = F,Cl, Br,I) |
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| Authors: | Jing‐Gang Gai Yi Ren |
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| Affiliation: | 1. College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China;2. College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of ChinaCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China |
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| Abstract: | Gas‐phase anionic reactions X? + CH3SY (X, Y = F, Cl, Br, I) have been investigated at the level of B3LYP/6‐311+G (2df,p). Results show that the potential energy surface (PES) of gas‐phase reactions X? + CH3SY (X, Y = Cl, Br, I) has a quadruple‐well structure, indicating an addition–elimination (A–E) pathway. The fluorine behaves differently in many respects from the other halogens and the reactions F? + CH3SY (Y = F, Cl, Br, I) correspond to deprotonation instead of substitution. The gas‐phase reactions X? + CH3SF (X = Cl, Br, I), however, follow an A–E pathway other than the last two out going steps (COM2 and PR) that proceeds via a deprotonation. The polarizable continuum model (PCM) has been used to evaluate the solvent effects on the energetics of the reactions X? + CH3SY (X, Y = Cl, Br, I). The PES is predicted to be unimodal in the solvents of high polarity. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 |
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| Keywords: | addition– elimination mechanism sulfur atom nucleophilic substitution DFT theory polarizable continuum model (PCM) |
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