• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >A Theoretician's View of the C-F Bond Activation Mediated by the Lanthanide Cations Ce~+ and Ho~+
【24h】

A Theoretician's View of the C-F Bond Activation Mediated by the Lanthanide Cations Ce~+ and Ho~+

机译：镧系阳离子Ce〜+和Ho〜+介导的C-F键活化的理论家观点

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The mechanistic details of the fluorine transfer reaction Ln~++F-R->LnF~++R with fluoromethane and fluroobenzene as substrates F-R have been elucidated by jusing quantum chemical techniques. We have chosen two lanthanide monocations, Ce~+ and Ho~+ as representatives for the early and rather reactive rare earth elements with low second ionization energy (IE)(Ce~+) and the late and less reactive elements possessing a higher second IE(Ho~+). The reaction path oif the defluorination process of the two fluorohydrocarbons CH_3F and C_6H_5F brought about by these cations was mapped by determining all relevant stationary points, that is,reactants, intermediates,saddle points, and products along the reaction coordinate. The occurrence of two competing different reaction paths is the key for a rationalization of the counterintuitive experimental observation of a higer reactivity fluorobenzene compared to fluoromethane in spite of itssignificantly larger C-F bond strength.
机译：利用量子化学技术阐明了以氟代甲烷和氟代苯为底物F-R的氟转移反应Ln〜++ F-R-> LnF〜++ R的机理细节。我们选择了两个镧系单阳离子Ce〜+和Ho〜+作为具有较低第二电离能（IE）（Ce〜+）的早期和相当活性的稀土元素以及具有较高第二IE的晚期和较少活性元素的代表（Ho〜+）。通过确定沿反应坐标系的所有相关固定点，即反应物，中间体，鞍点和产物，确定了由这些阳离子引起的两种氟代烃CH_3F和C_6H_5F的脱氟过程的反应路径。尽管存在显着较大的C-F键强度，但发生两个竞争性不同反应路径的问题是合理化与氟甲烷相比具有更高反应活性的氟苯与实验相反的实验观察结果的关键。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号