X-ray crystallography of iron-hydrogenases reveals that the active-site H-c
luster contains an unmistakably organometallic dinuclear iron subcluster. T
he nickel-hydrogenases, which in general play different metabolic roles, ha
ve a distinct but related active-site structure. The new structural definit
ion, combined with chemical analogs and theoretical treatment, points towar
d mechanistic understanding of iron-hydrogenases and the possibility of a u
nified mechanism for all hydrogenases.