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Article

Properties and Reactivity of Chlorovinylcobalamin and Vinylcobalamin and Their Implications for Vitamin B₁₂-Catalyzed Reductive Dechlorination of Chlorinated Alkenes

Supporting Info

Kevin M. McCauley,^† Derek A. Pratt,^† Scott R. Wilson,^†^‡ Justin Shey,^† Theodore J. Burkey,^§ and Wilfred A. van der Donk*^†

Contribution from the Departments of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois, and University of Memphis, Smith Chemistry Building, Memphis, Tennessee 38152

J. Am. Chem. Soc., 2005, 127 (4), pp 1126–1136

DOI: 10.1021/ja048573p

Publication Date (Web): January 8, 2005

†

University of Illinois at Urbana-Champaign.

‡

To whom correspondence regarding crystallography should be addressed.

University of Memphis.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, vddonk@uiuc.edu

Abstract

Vitamin B₁₂-catalyzed reductive dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) is a potential strategy for cleanup of polluted environments. Presented are crystal structures of vinylcobalamin 2 and cis-chlorovinylcobalamin 1. They show a strong resistance toward photolysis. Reduction of 2 is difficult, but reduction of 1 occurs readily and produces 2. The mechanism of this latter reaction involves acetylene as an intermediate. These and other findings are discussed in the context of environmental studies on B₁₂-catalyzed dechlorination of PCE and TCE and investigations of the haloalkene reductive dehalogenases that catalyze similar reactions.

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History

Published In Issue February 02, 2005
Received March 11, 2004
Revised November 14, 2004

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Article

Properties and Reactivity of Chlorovinylcobalamin and Vinylcobalamin and Their Implications for Vitamin B₁₂-Catalyzed Reductive Dechlorination of Chlorinated Alkenes