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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanism of Abstraction Reactions of Heavy Cyclopropenes with Carbon Tetrachloride
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Mechanism of Abstraction Reactions of Heavy Cyclopropenes with Carbon Tetrachloride

机译：重环丙烯与四氯化碳抽象反应的机理

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摘要

The potential energy surfaces for the abstraction reactions of heavy cyclopropenes (X-Y-Z) with carbon tetrachloride have been characterized in detail using density functional theory (B3LYP), including zero-point corrections. Five cyclopropene analogues including A(C-C-C), B(Ge-Si-Si), C(Si-Si-Si), D(Si-Si-Ge), and E(Ge-Ge-Ge), have been chosen in this work as model reactants. Two reaction paths, the Cl abstraction I and the CCl3 abstraction II, have been considered in the present study. Our theoretical findings strongly suggest that the former is more favorable, with a very low activation energy and a large exothermicity. This is in accordance with available experimental observations. Moreover, our theoretical investigations also indicate that the more electropositive the elements making up the double bond of a heavy cyclopropene, the lower its activation barrier and the more exothermic the haloalkane abstraction. That is, electronic factors play a dominant role in determining the chemical reactivity of the heavy cyclopropene species kinetically as well as thermodynamically. Furthermore, a configuration mixing model based on the work of Pross and Shaik is used to rationalize the computational results. The results obtained allow a number of predictions to be made.
机译：重密度环丙烯（X-Y-Z）与四氯化碳抽象反应的势能面已使用密度泛函理论（B3LYP）进行了详细表征，包括零点校正。已从中选择了五个环丙烯类似物，包括A（CCC），B（Ge-Si-Si），C（Si-Si-Si），D（Si-Si-Ge）和E（Ge-Ge-Ge）。用作模型反应物。在本研究中考虑了两个反应路径，即Cl抽象I和CCl3抽象II。我们的理论发现强烈表明，前者是更有利的，具有非常低的活化能和较大的放热性。这与现有的实验观察一致。而且，我们的理论研究还表明，构成重环丙烯的双键的元素带正电性越强，其活化势垒越低，卤代烷烃的抽象放热越大。即，电子因素在动力学和热力学上决定重环丙烯种类的化学反应性中起主要作用。此外，基于Pross和Shaik的工作的配置混合模型用于合理化计算结果。获得的结果使得可以做出许多预测。

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