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

页码：557 / 565

页数：9

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