Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (11): 1245-1249.DOI: 10.6023/A1201134 Previous Articles     Next Articles

Full Papers

Fe2+活化CH3X (X=H, Cl)中C—H, C—Cl 键的理论研究

孙小丽, 李吉来, 黄旭日, 孙家锺   

  1. 吉林大学理论化学研究所 理论化学国家重点实验室 长春 130023
  • 投稿日期:2012-01-13 修回日期:2012-02-28 发布日期:2012-03-29
  • 通讯作者: 李吉来, 黄旭日
  • 基金资助:

    国家自然科学基金(Nos. 21103064, 21073075 和21173097)、教育部博士点基金(No. 20100061110046)、吉林大学理论化学国家重点实验室专项基金和吉林大学基本科研业务费(Nos. 421010061439, 450060445067).

A Theoretical Study on Activation of C—H and C—Cl Bonds in CH3X (X=H, Cl) by Fe2+

Sun Xiaoli, Li Jilai, Huang Xuri, Sun Chiachung   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023
  • Received:2012-01-13 Revised:2012-02-28 Published:2012-03-29
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21103064, 21073075, 21173097), Research Fund for the Doctoral Program of Higher Education of China (No. 20100061110046), the Special Funding of State Key Laboratory of Theoretical and Computational Chemistry, Jilin University and Basic Research Fund of Jilin University (Nos. 421010061439, 450060445067).

The reactions of Fe2+ with CH3X (X=H, Cl) have been studied by density functional theory method detailedly. The results demonstrated that the H abstraction in Eq. 4 can proceed via the lowest activation barrier (ΔGa=0.23 kcal/mol) in all feasible pathways. However, the mechanisms of oxidative insertion and the SN2 substitution are not competitive because of thermodynamic factors. The electronic structure analysis suggests that the overlap between metal 3d orbital and substrate σC—X* results in the preference of Fe2+ front side attack on the C—X bond. This study is expected to shed light on the nature of the title reactions and provide theoretical clues and foundation for future research.

Key words: SN2, insertion, abstraction, reaction mechanism, activation barrier, electronic structure