Theoretical study of the gas‐phase ion pairs SN2 reactions of LiX with CH3SY (X,Y = F,Cl, Br,I) |
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| Authors: | Jing‐Gang Gai Yi Ren |
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| Institution: | 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: | The gas‐phase ion pair SN2 reactions at saturated sulfur LiX + CH3SY → CH3SX + LiY (X, Y = F, Cl, Br, I) are investigated using the CCSD(T) calculations. The calculated results show that the reactions LiX + CH3SY are exothermic only when the nucleophile is a heavier lithium halide. Central barrier heights are found to depend primarily on the identity of nucleophile LiX, decreasing in the order LiF > LiCl > LiBr > LiI. Another interesting feature of the ion pair reactions at sulfur is the good correlation between the reaction barriers with geometrical looseness of Li? X and S? Y bonds in the transition state structures. The data for the reaction barriers show good agreement with the prediction of the Marcus equation and its modification. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 |
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| Keywords: | ion pair SN2 reaction sulfur atom |
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