Activation of dihydrogen is by far not a trivial catalytic reaction. Microbes have evolved sophisticated hydrogenases with complex transition metal centers to get access to dihydrogen (H2). A recurring feature of these centers is the presence of iron atoms equipped with carbon monoxide ligands. In case of [NiFe]-hydrogenases, which contain a NiFe(CN)2CO catalytic center, biosynthesis of the toxic CO ligand remained elusive.
Oliver Lenz, Ingo Zebger and colleagues show for the first time that [NiFe]-hydrogenases that are catalytically active in the presence of dioxygen use a dedicated maturase for CO ligand synthesis under aerobic conditions. CO is derived from the most oxidized intermediate of the central one-carbon metabolism, formyl-tetrahydrofolate. This discovery contributes a so far unknown reaction to the one-carbon metabolism and opens perspectives for chemical and of bioinspired catalysis.
CO synthesized from the central one-carbon pool as source for the iron carbonyl in O2-tolerant [NiFe]-hydrogenase
Ingmar Bürstel, Elisabeth Siebert, Stefan Frielingsdorf, Ingo Zebger, Bärbel Friedrich, Oliver Lenz
Proc. Natl. Acad. Sci. U. S. A. 2016, published online 5 December 2016