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A unifying structural and electronic concept for Hmd and [FeFe] hydrogenase active sites
Martin T Stiebritz1, Markus Reiher
1Laboratorium für Physikalische Chemie, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
Abstract:
The hydrogenases [FeFe] and Hmd feature at first sight rather different active sites. A closer inspection reveals striking similarities, which allow us to define swapped ligand spheres in such a way that the single active iron center of Hmd functions in a first-shell ligand environment resembling the reacting iron atom in [FeFe] hydrogenase and vice versa. These redesigned ligand environments can be conveniently studied with quantum chemical methods and point to general reactivity principles for iron centers with hydrogenase activity.
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