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The estimate of slightly different reduction potentials for dissociative electron transfer to TCE producing cis- or trans-dichloroethenyl radicals in ref 27 is based on different values for Henry's constant while assuming identical heats of formation. Although we arrive at a similar overall conclusion with respect to more facile reduction to the cis-dichloroethenyl radical, our conclusion is based on significantly different energies/enthalpies for the gas-phase species.
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Cob(II)alamin, formed after one-electron donation in the dissociative electron transfer to TCE, is not included in the optimized geometries shown in Figure 1. The relative energies of 12 and 15 might very well be modulated by its presence to bring the energy difference closer to that observed for 4 and 5.
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57
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a of the methanol radical is 10.6; Henglein, A. Adv. Electroanal. Chem. 1976, 9, 163), and a strongly reducing ketyl radical anion may be formed (E° ≈ -2.5 V for the isopropyl ketyl radical anion; Wardman, P. J. Phys. Chem. Ref. Data 1989, 18, 1691). This ketyl radical anion may then be the reducing agent that converts the vinyl radicals to their anions. It should be noted that the possibly artificially increased percentage of products derived from anions did not alter the high selectivity for cis products in these studies.
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Henglein, A.1
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a of the methanol radical is 10.6; Henglein, A. Adv. Electroanal. Chem. 1976, 9, 163), and a strongly reducing ketyl radical anion may be formed (E° ≈ -2.5 V for the isopropyl ketyl radical anion; Wardman, P. J. Phys. Chem. Ref. Data 1989, 18, 1691). This ketyl radical anion may then be the reducing agent that converts the vinyl radicals to their anions. It should be noted that the possibly artificially increased percentage of products derived from anions did not alter the high selectivity for cis products in these studies.
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A second possible source of chloroacetylene would be from chloroethenylcobalamins. See refs 44 and 45.
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Similar to the product distribution from ethenyl radicals, the ratio of the products derived from vinyl anions will be dependent on the barriers of interconversion and protonation. However, the latter is expected to be relatively low compared to the high interconversion energy barrier.
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83
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84889546324
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in press
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12-catalyzed dechlorination of PCE and TCE. If thc cis and trans radicals have similar reduction potentials, then the high interconversion barrier for 26 and 27 maintains overall cis selectivity. However, if the reduction potential for trans radical 5 is significantly different from that for cis radical 4 and the reduction of the radicals to their anions is significantly faster than other transformations of these species, then the final product ratio is solely dependent on the relative reduction potentials of 4 and 5. Such selective reduction of isomeric radicals has, in fact, been reported to determine the product ratio in the reductive dechlorination of 1,1,2,2-tetrachloroethane: Arnold, W.A.; Winget, P.; Cramer, C.J. Environ. Sci. Technol., in press.
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