title: One-electron-transfer reactions of polychlorinated ethylenes: concerted and stepwise cleavages.
abstract: Reaction barriers were calculated by using ab initio electronic structure methods for the reductive dechlorination of the polychlorinated ethylenes: C2Cl4, C2HCl3, trans-1,2-C2H2Cl2, cis-1,2-C2H2Cl2, 1,1-C2H2Cl2 and C2H3Cl. Concerted and stepwise cleavages of R-Cl bonds were considered. Stepwise cleavages yielded lower activation barriers than concerted cleavages for the reduction of C2Cl4, C2HCl3, 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-C2HCl2* over the formation of trans-1,2-C2HCl2*, and 1,1-C2HCl2* radicals.
authors: Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA.
authors: Eric J
authors: EJ
authors: Bylaska
authors: Michel
authors: M
authors: Dupuis
authors: Paul G
authors: PG
authors: Tratnyek
mesh_terms: D004579:Electron Transport; D005030:Ethylenes / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D005030:Ethylenes; D006843:Hydrocarbons, Chlorinated