PT  - JOURNAL ARTICLE
AU  - Reissmann, Stefanie
AU  - Hochleitner, Elisabeth
AU  - Wang, Haofan
AU  - Paschos, Athanasios
AU  - Lottspeich, Friedrich
AU  - Glass, Richard S.
AU  - Böck, August
TI  - Taming of a Poison: Biosynthesis of the NiFe-Hydrogenase Cyanide Ligands
AID  - 10.1126/science.1080972
DP  - 2003 Feb 14
TA  - Science
PG  - 1067--1070
VI  - 299
IP  - 5609
4099  - http://science.sciencemag.org/content/299/5609/1067.short
4100  - http://science.sciencemag.org/content/299/5609/1067.full
SO  - Science2003 Feb 14; 299
AB  - NiFe-hydrogenases have an Ni-Fe site in which the iron has one CO and two CN groups as ligands. Synthesis of the CN ligands requires the activity of two hydrogenase maturation proteins: HypF and HypE. HypF is a carbamoyltransferase that transfers the carbamoyl moiety of carbamoyladenylate to the COOH-terminal cysteine of HypE and thus forms an enzyme-thiocarbamate. HypE dehydrates theS-carbamoyl moiety in an adenosine triphosphate–dependent process to yield the enzyme thiocyanate. Chemical model reactions corroborate the feasibility of this unprecedented biosynthetic route and show that thiocyanates can donate CN to iron. This finding underscores a striking parallel between biochemistry and organometallic chemistry in the formation of an iron-cyano complex.