期刊
ACS CENTRAL SCIENCE
卷 4, 期 10, 页码 1430-1435出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscentsci.8b00553
关键词
-
资金
- NSF [CHE-1608926]
Isolated nitrogenase cofactors can reduce CO, CN-, and CO2 to short-chain hydrocarbons in reactions driven by a strong reductant. Here, we use activity analyses and isotope labeling experiments to show that formaldehyde and acetaldehydes can be reduced as-is or reductively condensed into alkanes and alkenes by the isolated cofactor of Mo-nitrogenase in the presence of EuII-diethylenetriamine pentaacetate (DTPA). Further, we demonstrate that aldehydes can be condensed with CO by the isolated cofactor under the same reaction conditions, pointing to aldehyde-derived species as possible intermediates of nitrogenase-catalyzed CO reduction. Our deuterium labeling experiments suggest the formation of a cofactor-bound hydroxymethyl intermediate upon activation of the formaldehyde, as well as the release of C2H4 as a product upon beta-hydride elimination of an acetaldehyde-derived hydroxyethyl intermediate. These findings establish the reductive condensation of aldehydes as a previously unobserved reactivity of a biogenic catalyst while at the same time shed light on the mechanism of enzymatic CO reduction and C-C bond formation, thereby providing a useful framework for further exploration of the unique reactivity and potential applications of nitrogenase-based reactions.
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