Evidence for the formation of a cis-dichlorovinyl anion upon reduction of cis-1,2-dichlorovinyl(pyridine)cobaloxime

Angela D. Follett, Kristopher McNeill

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

The reduction of cis-1,2-dichlorovinyl(pyridine)cobaloxime, a model complex for the organometallic intermediate proposed in the dechlorination of trichloroethylene by cobalamin, was studied. Two mechanisms were considered for the Co-C bond cleavage following reduction. In the first, the Co-C bond cleaves to produce CoI and a chlorovinyl radical, while the second pathway results in the formation of CoII and a chlorovinyl anion. Four reducing agents, cobaltocene, decamethylcobaltocene, cob(I)alamin, and chromium(II), were used in the presence of H atom and proton donor species to identify the presence of chlorovinyl radical or chlorovinyl anion intermediates. Mechanistic conclusions were based on comparisons of the final product ratios of cis-dichloroethylene (cDCE) and chloroacetylene, which were found to have a direct relationship to the amount of proton donor available, with increased proton donor leading to increased cDCE production. The results support the intermediacy of a cis-1,2-dichlorovinyl anion.

Original languageEnglish (US)
Pages (from-to)2727-2732
Number of pages6
JournalInorganic Chemistry
Volume45
Issue number6
DOIs
StatePublished - Mar 20 2006

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