Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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CCl4 Activation Mechanisms by Gas-Phase CHBr•– and CBr2•–: A Comparative Study

  • Liang, Junxi (College of Chemical Engineering, Northwest University for Nationalities) ;
  • Wang, Yanbin (College of Chemical Engineering, Northwest University for Nationalities) ;
  • Hasi, Qimeige (Science Experimental Center, Northwest University for Nationalities) ;
  • Geng, Zhiyuan (Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Key Laboratory of Eco-environment-related Polymer Materials)
  • Received : 2012.08.31
  • Accepted : 2012.11.12
  • Published : 2013.02.20
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Abstract

The mechanisms concerning C-Cl activation of $CCl_4$ by $CHBr^{{\cdot}-}$ and $CBr{_2}^{{\cdot}-}$ have been comparatively investigated in theory. Optimized geometries and frequencies of all stationary points on PES are obtained at the BhandHLYP/aug-cc-pVTZ level of theory, and then the energy profiles are refined at the QCISD(T) method with the aug-cc-pVTZ basis by using the BhandHLYP/aug-cc-pVTZ optimized geometries. Our calculated findings suggest that in the title reactions the major mechanisms consist of both Cl-abstraction and $S_N2$ substitution reactions. Also, a succeeding pathway described by electron transfer was revealed before the initial Cl-abstraction products separate. Those are consistent with relevant experimental results.

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References

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