Cl4 Activation Mechanisms by Gas-Phase CHBr•– and CBr2 size='2'>•–: A Comparative Study

摘要

The mechanisms concerning C-Cl activation of CCl4 by CHBr•– and CBr2 •– 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 SN2 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.