Reductive formation of carbon monoxide from CCl sub 4 and FREONs 11, 12, and 13 catalyzed by corrinoids

Journal Article · Mon Mar 11 23:00:00 EST 1991 · Biochemistry; (United States)

DOI:https://doi.org/10.1021/bi00224a020· OSTI ID:5081525

Krone, U E; Thauer, R K; Steinbach, K ^[1]; Hogenkamp, H P.C. ^[2]

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1. Philipps-Univ., Marburg (West Germany)
2. Univ. of Minnesota, Minneapolis (United States)

In an earlier publication, the authors reported that corrinoids catalyze the sequential reduction of CCl{sub 4} to CHCl{sub 3}, CH{sub 2}Cl{sub 2}, CH{sub 3}Cl, and CH{sub 4} with titanium (III) citrate as electron donor. However, the recovery of these products was less than 50% indicating that other products were formed. The authors now report that, under the same experimental conditions, CCl{sub 4} is also converted to carbon monoxide. These studies were extended to include FREONs 11,12,13, and 14. Corrinoids were found to catalyze the reduction of CFCl{sub 3}, CF{sub 2}Cl{sub 2}, and CF{sub 3}Cl to CO and, in the case of CFCl{sub 3}, to a lesser extent, to formate. CF{sub 4} was not reduced. The rate of CO and formate formation paralleled that of fluoride release. Both rates decreased in the series CFCl{sub 3}, CF{sub 2}Cl{sub 2}, CCl{sub 4}, and CF{sub 3}Cl. The reduction of CFCl{sub 3} gave, in addition to CO and formate, CHFCl{sub 2}, CH{sub 2}FCl, CH{sub 3}F, C{sub 2}F{sub 2}Cl{sub 2}, and C{sub 2}F{sub 2}Cl{sub 4}. The product pattern indicates that the corrinoid-mediated reduction of halogenate C{sub 1}-hydrocarbons involves the intermediacy of dihalocarbenes, which may be a reason why these compounds are highly toxic for anaerobic bacteria.

• DOE Contract Number: FG02-89ER14013
• OSTI ID: 5081525
• Journal Information: Biochemistry; (United States), Journal Name: Biochemistry; (United States) Vol. 30:10; ISSN 0006-2960; ISSN BICHA
• Country of Publication: United States
• Language: English

Related Subjects

550200* -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
ANAEROBIC CONDITIONS
BACTERIA
BIOSYNTHESIS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBON TETRACHLORIDE
CARBOXYLIC ACID SALTS
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CITRATES
FREONS
HALOGENATED ALIPHATIC HYDROCARBONS
METHYLENE CHLORIDE
MICROORGANISMS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REDUCTION
SYNTHESIS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS