The iron of the binuclear active center of [NiFe]-hydrogenases carries two
CN and one CO ligands which are thought to confer to the metal a low oxidat
ion and/or spin state essential for activity. Based on the observation that
one of the seven auxiliary proteins required for the synthesis and inserti
on of the [NiFe] cluster contains a sequence motif characteristic of O-carb
amoyl-transferases it was discovered that carbamoyl phosphate is essential
for formation of active [NiFe]-hydrogenases in vivo and is specifically req
uired for metal center synthesis suggesting that it is the source of the CO
and CN ligands, A chemical path for conversion of a carbamoyl group into c
yano and carbonyl moieties is postulated. (C) 2001 Federation of European B
iochemical Societies, Published by Elsevier Science B.V. All rights reserve
d.