TY - JOUR
T1 - One-electron-transfer reactions of polychlorinated ethylenes
T2 - Concerted and stepwise cleavages
AU - Bylaska, Eric J.
AU - Dupuis, Michel
AU - Tratnyek, Paul G.
N1 - Copyright:
Copyright 2011 Elsevier B.V., All rights reserved.
PY - 2008/4/24
Y1 - 2008/4/24
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=44949208578&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=44949208578&partnerID=8YFLogxK
U2 - 10.1021/jp711021d
DO - 10.1021/jp711021d
M3 - Article
C2 - 18366197
AN - SCOPUS:44949208578
SN - 1089-5639
VL - 112
SP - 3712
EP - 3721
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 16
ER -