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| 高位阻烷烃的C-C和C-H键的键离解能 | |
| 引用本文： | 朱晨,芮蕾,傅尧. 高位阻烷烃的C-C和C-H键的键离解能[J]. 中国化学, 2008, 26(8): 1493-1500. DOI: 10.1002/cjoc.200890270 |
| 作者姓名： | 朱晨 芮蕾 傅尧 |
| 作者单位： | 中国科学技术大学化学系，合肥 230026 |
| 摘 要： | 本文使用ONIOM-G3B3的方法计算了一系列高位阻烷烃的C-C和C-H键离解能。研究还测定了它们的几何参数,如键长,键角,分子体积等,它们中的绝大多数分子目前还没有被合成。这些几何参数表征了位阻效应对键离解能产生的影响。研究确定了键离解能的迅速减小和分子体积的增大之间的一些关系。这些关系可以帮助使用理论方法预测很多高位阻化合物的合成。 |
| 关 键 词： | 键离解能；脂肪族烷烃；位阻效应；几何参数；ONIOM-G3B3 |
| 收稿时间： | 2007-12-29 |
| 修稿时间： | 2008-03-23 |
Homolytic Bond Dissociation Enthalpies of C–C and C–H Bonds in Highly Crowded Alkanes |
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| Chen ZHU,Lei RUI,Yao FU. Homolytic Bond Dissociation Enthalpies of C–C and C–H Bonds in Highly Crowded Alkanes[J]. Chinese Journal of Chemistry, 2008, 26(8): 1493-1500. DOI: 10.1002/cjoc.200890270 | |
| Authors: | Chen ZHU Lei RUI Yao FU |
| Affiliation: | 1. Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China;2. Fax: 0086‐0551‐3606689 |
| Abstract: | The homolytic C–C and C–H bond dissociation enthalpyies (BDE) of highly crowded alkanes were calculated by using an ONIOM‐G3B3 method. Geometric parameters such as bond length, bond angle and molecular volume were carefully investigated, as most of the acyclic alkanes in this study were not yet synthesized. These parameters reflect the influence of steric effect on BDE. Good correlations were found between the rapid decrease of BDE and the increase of molecular volumes. The correlations can be applied to the prediction of the possible existence of many highly strained compounds. |
| Keywords: | bond dissociation enthalpy acyclic alkane steric effect geometric parameter ONIOM‐G3B3 |
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