DFT study on the reaction mechanisms of polyfluorosulfonate ester with F- reaction

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	DFT study on the reaction mechanisms of polyfluorosulfonate ester with F- reaction
	Guo L(郭丽) ; Yu ZH(虞忠衡) ; Zhu SZ(朱仕正) ; Chen QY(陈庆云)
刊名	Theochem-J. Mol. Struct.
	2005
卷号	730 期号:1-3 页码:143-150
ISSN号	0166-1280
其他题名	DFT研究多氟磺酰酯和氟负离子的反应
英文摘要	Gas-phase reaction of Q(1)F3S(2)O2O(3)Q4)H2C((5))F-3 and F-(16) is investigated using DIFT method. The geometries of various stationary points and their relative energies are obtained from 6-31 + G, 6-31 1G, and 6-311 + + G* levels. In the S(N)2(C) reaction leading to the cleavage of the C(4)-O(3) bond, the reaction complex results from attacking of F- at a hydrogen atom H11 attached to carbon atom C(4). Afterward, F- is attacking the atom C(4) from the backside of the atom O(3) with the help of the neighboring effect, and meanwhile a multi-membered ring, F(16)-H(11)-C(4)-C(5)-F(16), is being formed. The S(N)2(C) reaction is irreversible. On the contrary, the S(N)2(S) reaction leading to the cleavage of the S(2)-O(3) bond is reversible, and it is initiated by attacking of F- at the atom S(2) from the backside of the atom O(3). The products of the reaction CF3SO3CH2CF3 +F- should be, thermodynamically, controlled due to the reversibility of the S(N)2(S) reaction, and those result, chemospecifically, from the cleavage of the C-O bond. At last, the SCRF calculations confirm that the solvent effect is preferable to the S(N)2(C) reaction. (c) 2005 Elsevier B.V. All rights reserved.
学科主题	有机氟化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1016/j.theochem.2005.06.013
语种	英语
公开日期	2013-01-17
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/13582]
专题	上海有机化学研究所_中科院有机氟化学重点实验室
推荐引用方式 GB/T 7714	Guo L,Yu ZH,Zhu SZ,et al. DFT study on the reaction mechanisms of polyfluorosulfonate ester with F- reaction[J]. Theochem-J. Mol. Struct.,2005,730(1-3):143-150.
APA	郭丽,虞忠衡,朱仕正,&陈庆云.(2005).DFT study on the reaction mechanisms of polyfluorosulfonate ester with F- reaction.Theochem-J. Mol. Struct.,730(1-3),143-150.
MLA	郭丽,et al."DFT study on the reaction mechanisms of polyfluorosulfonate ester with F- reaction".Theochem-J. Mol. Struct. 730.1-3(2005):143-150.