Reconciling disparate models of the involvement of vinyl radicals in cobalamin-mediated dechlorination reactions

Environmental Science & Technology
Sarah Kliegman, Kristopher McNeill

Abstract

Inner-sphere (nonradical) and outer-sphere (radical-based) mechanisms have been suggested for cobalamin-mediated dechlorination of tetrachloroethylene (PCE) and trichloroethylene (TCE). In this study, the role of free vinyl radicals was investigated using deuterated radical traps: d(8)-isopropanol and d(8)-tetrahydrofuran. For both substrates, addition of trap resulted in production of deuterated dechlorination products, and higher concentrations of trap resulted in increased amounts of deuterated products. However, only a finite proportion of the products were trappable: 8% of the PCE-derived products and 86% of the TCE-derived products result from free radicals. The data show that the reaction does not proceed solely by either an inner-sphere or an outer-sphere mechanism and led to the hypothesis that caged radical intermediates were involved in the mechanism. The untrappable fraction of products are hypothesized to result from in-cage reactions. This hypothesis was investigated using d(5)-glycerol as a radical trap and viscogen. Although increased viscosity resulted in decreased formation of free-radical-derived products, consistent with the cage hypothesis, these data were inconclusive. The role of d(8)-isopropanol in enhan...Continue Reading

References

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Jan 20, 2005·Journal of the American Chemical Society·Angela D Follett, Kristopher McNeill
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Feb 9, 2007·Inorganic Chemistry·Angela D FollettKristopher McNeill
Aug 7, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Sarah Kliegman, Kristopher McNeill

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Citations

May 24, 2014·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Stefan CretnikMartin Elsner
Jul 22, 2015·Environmental Science & Technology·Marco RattiThomas B Hofstetter
Jun 3, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Heinz Berke
May 30, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Emily J PeltonKristopher McNeill

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