PuSH - Publication Server of Helmholtz Zentrum München: Reductive outer-sphere single electron transfer is an exception rather than the rule in natural and engineered chlorinated ethene dehalogenation.

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Heckel, B. ; Cretnik, S. ; Kliegman, S.* ; Shouakar-Stash, O.* ; McNeill, K.* ; Elsner, M.

Reductive outer-sphere single electron transfer is an exception rather than the rule in natural and engineered chlorinated ethene dehalogenation.

Environ. Sci. Technol. 51, 9663-9673 (2017)

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Chlorinated ethenes (CEs) such as perchloroethylene, trichloroethylene and dichloroethylene are notorious groundwater contaminants. Although reductive dehalogenation is key to their environmental and engineered degradation, underlying reaction mechanisms remain elusive. Outer-sphere reductive single electron transfer (OS-SET) has been proposed for such different processes as Vitamin B 12 -dependent biodegradation and zerovalent metal-mediated dehalogenation. Compound-specific isotope effect ( 13 C/ 12 C, 37 Cl/ 35 Cl) analysis offers a new opportunity to test these hypotheses. Defined OS-SET model reactants (CO 2 radical anions, S 2- -doped graphene oxide in water) caused strong carbon (ε C = -7.9‰ to -11.9‰), but negligible chlorine isotope effects (ε Cl = -0.12‰ to 0.04‰) in CEs. Greater chlorine isotope effects were observed in CHCl 3 (ε C = -7.7‰, ε Cl = -2.6‰), and in CEs when the exergonicity of C-Cl bond cleavage was reduced in an organic solvent (reaction with arene radical anions in glyme). Together, this points to dissociative OS-SET (SET to a σ∗ orbital concerted with C-Cl breakage) in alkanes compared to stepwise OS-SET (SET to a π∗ orbital followed by C-Cl cleavage) in ethenes. The nonexistent chlorine isotope effects of chlorinated ethenes in all aqueous OS-SET experiments contrast strongly with pronounced Cl isotope fractionation in all natural and engineered reductive dehalogenations reported to date suggesting that OS-SET is an exception rather than the rule in environmental transformations of chlorinated ethenes.

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