ic060075p_si_001.pdf (1.05 MB)
Resolving the CO/CN Ligand Arrangement in CO-Inactivated [FeFe] Hydrogenase by First Principles Density Functional Theory Calculations
journal contribution
posted on 2006-07-24, 00:00 authored by Silviu Zilberman, Edward I. Stiefel, Morrel H. Cohen, Roberto CarThe currently presumed assignment of CO/CN ligands in the
structure of the active cluster in CO-inactivated [FeFe] hydrogenase
is shown to be inconsistent with the available IR data in the enzyme
from Clostridium pasteurianum I. A different arrangement has the
correct qualitative and quantitative features, reproducing the
observed line spacing and intensities and the observed line shift
consequent to inactivation with labeled 13CO instead of 12CO. The
new assignment is also consistent with the observed change from
rhombic to axial symmetry of the electron paramagnetic resonance
g tensor upon inactivation.