Computational studies of [NiFe] and [FeFe] hydrogenases. uri icon

abstract

  • The [NiFe] enzymes are primarily utilized for hydrogen oxidation while the [FeFe] enzymes are primarily utilized for proton reduction. Obtained from Desulfovibrio (D.) gigas, using the combined quantum mechanics and molecular mechanics (QM/MM) models, the computations on [NiFe] hydrogenase have been done. The heterolytic cleavage of the H-H bond leads to bridging hydride and a protonated terminal Cys492, followed by a transition state. In calculating the [FeFe] hydrogenase models strongly support a cycle that involves reduction of the FeIFeII resting form to the FeIFeI form then capture of a proton by the metal, an event that oxidizes the metals to an FeIIFeII form. The second proton and electron transfer produces dihydrogen and regenerates the FeIFeII form. The calculations favored the geometry for the reduced state and the geometry observed in synthetic model complexes.

published proceedings

  • Chem Rev

author list (cited authors)

  • Siegbahn, P., Tye, J. W., & Hall, M. B.

citation count

  • 374

complete list of authors

  • Siegbahn, Per EM||Tye, Jesse W||Hall, Michael B

publication date

  • October 2007