Ab initio investigation of the O-H insertion reactions of CH2X-X (X = Cl, Br, I) isopolyhalomethanes with water

被引：10
|
作者：
Li, YL [1 ]
Zhao, C [1 ]
Guan, X [1 ]
Phillips, DL [1 ]
机构：
[1] Univ Hong Kong, Dept Chem, Hong Kong, Hong Kong, Peoples R China
来源：
RESEARCH ON CHEMICAL INTERMEDIATES | 2005年 / 31卷 / 7-8期
关键词：
Ab initio; O-H insertion; isopolyhalomethanes; substituent effect;
D O I：
10.1163/1568567054909104
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Here, we report ab initio calculations for the O-H insertion reactions of CH2X-X (X = Cl, Br, I) with H2O and examine substituent effects for changing the halogen atom. As Cl changes to Br and then I, the O-H insertion reactions lead to an HX acid leaving group and range from about 2.3 kcal/mol for X = Cl to about 16.3 kcal/mol for X = I. We compare the trends as the halogen atom varies from Cl to Br and I in the O-H insertion reactions of CH2X-X with H2O to the cyclopropanation reactions of CH2X-X with ethylene. We very briefly discuss possible implications for phase-dependent photochemistry of polyhalomethanes in the atmosphere.
引用
收藏
页码：557 / 565
页数：9
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