Reaction barriers were calculated by using ab initio electronic structure mediods for the reductive dechlorination of the polychlorinated ethylenes: C2Cl4, C2HCl3, trans-1,2-C 2H2Cl2, cis-1,2-C2H 2Cl2, 1,1-C2H2Cl2 and C2H3-Cl. Concerted and stepwise cleavages of R-Cl bonds were considered. Stepwise cleavages yielded lower activation barriers than concerted cleavages for the reduction of C2CU, C2HCl 3, and trans-1,2-C2H2Cl2 for strong reducing agents. However, for typical ranges of reducing strength concerted cleavages were found to be favored. Both gas-phase and aqueous-phase calculations predicted C2Cl4 to have the lowest reaction barrier. Additionally, the reduction of C2HCl3 was predicted to show selectivity toward formation of cis-1,2-C2HCl 2· over the formation of trans-1,2-C2HCl 2·', and 1,1-C2HCl2· radicals.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry