Mechanistic aspects of the activation of C–H bond in C<sub class="a-plus-plus">2sub>H<sub class="a-plus-plus">6sub> by Th atom: bonding analysis and reaction coefficients

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• 作者：Qingqing Wang ; Peng Li ; Tao Gao ; Bingyun Ao
• 关键词：Atoms in molecules ; C–H activation ; Electron localization function ; Natural bond orbital ; Variational transition state theory
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2016
• 出版时间：December 2016
• 年：2016
• 卷：135
• 期：12
• 全文大小：1,458 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Theoretical and Computational Chemistry
  Inorganic Chemistry
  Organic Chemistry
  Physical Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1432-2234
• 卷排序：135

文摘

Density functional theory (DFT) calculations have been performed to investigate the reactivity of Th atom toward ethane C–H bond activation. To get the mechanism of the C–H bond activation by C<sub>2sub>H<sub>6sub>, a systematic DFT computational study is implemented. Comprehensive description of the reaction mechanism in the consideration of the possible spin states as well as analysis of the electronic factors offers detail information of C–H bond activation. The results indicate that the final reaction products of C–H breakage are the ThC<sub>2sub>H<sub>3sub> and ThC<sub>2sub>H<sub>2sub>. The nature of the bonding evolution along the reaction pathways was explored using distinct analysis method including electron localization function, atoms in molecules and natural bond orbital. Reaction rate constants were computed between 298 and 1000 K at levels of variational transition state theory for the first time.