title: Characterization of chlorovinylcobalamin, a putative intermediate in reductive degradation of chlorinated ethylenes.
abstract: The first X-ray structure of a vinylcobalamin is reported. Chlorovinylcobalamin is formed in the reaction of cob(I)alamin with chloroacetylene. Subsequently, cob(I)alamin catalyzes the reduction of chlorovinylcobalamin to vinylcobalamin in the presence of excess titanium(III)citrate. Introduction of a chlorine onto the vinyl group of vinylcobalamin greatly changes its reduction potential. These results are discussed with respect to vitamin B12-catalyzed dechlorination of perchloroethylene, a pollutant on the priority list of the EPA.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801, USA.
authors.forename: Kevin M
authors.initials: KM
authors.lastname: McCauley
authors.forename: Scott R
authors.initials: SR
authors.lastname: Wilson
authors.forename: Wilfred A
authors.initials: WA
authors.lastname: van der Donk
mesh_terms: D018360:Crystallography, X-Ray; D005030:Ethylenes / Q000737:chemistry*; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D010084:Oxidation-Reduction; D014753:Vinyl Compounds / Q000737:chemistry*; D014805:Vitamin B 12 / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D005030:Ethylenes; D006843:Hydrocarbons, Chlorinated; D014753:Vinyl Compounds; C474538:chlorovinylcobalamin; D014805:Vitamin B 12