Mechanism of Cobalamin-Mediated Reductive Dehalogenation of Chloroethylenes

Li Ji, Chenchen Wang, Shujing Ji, Kasper Planeta Kepp, Piotr Paneth

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Reductive dehalogenation involvingcobalamin has been proved to be a promising strategy for decontamination of the polluted environment. However, cob(I)alamin can act both as a strong reductant and a powerful nucleophile, and thus, several competing dehalogenation pathways may be involved. This work uses experimentally calibrated density functional theory on a realistic cobalamin model to resolve controversies of cobalamin-mediated reduction of chloroethylenes by exploring mechanisms of electron transfer, nucleophilic substitution, and nucleophilic addition. The computational results provide molecular-level insight into the competing pathways for chloroethylenes reacting with cob(I)alamin: the computed ratios of inner-sphere to outer-sphere pathways for perchloroethylene and trichloroethylene are 17:1 and 3.5:1, respectively, in accord with the corresponding experimental ratios of >10:1 and >2.3:1,whilethe computed outer-sphere pathway for other less-chlorinated ethylenesis hampered by high barriers (>25 kcal/mol). Thus, a new mechanistic picture has been obtained in which the highly chlorinated ethylenes primarily react via an inner-sphere nucleophilic-substitution pathway, whereas the less-chlorinated ethylenes mainly react through an inner-spherenucleophilic-addition pathway. Especially, the quantitative comparison of standard reduction potentials between the formed chlorinated-cobalamin and cob(II)alamin/cob(I)alamin couple can be used to distinguish whether the inner-sphere pathway can proceed or not, and linear free-energy relationships have been developed to predict the reductive dehalogenation reactivity within a given mechanism. Finally, we propose new dual-isotope analyses for distinguishing the various environmental dehalogenation mechanisms.
Original languageEnglish
JournalA C S Catalysis
Issue number8
Pages (from-to)5294-5307
Publication statusPublished - 2017


  • Reductive dehalogenation
  • Cobalamin
  • Density functional theory
  • Reduction potential
  • Inner-sphere pathway
  • Dual-isotope analyses


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