Modeling the active sites of metalloenzymes. 4. Predictions of the unreadystates of [NiFe] Desulfovibrio gigas hydrogenase from density functional theory
Sh. Li et Mb. Hall, Modeling the active sites of metalloenzymes. 4. Predictions of the unreadystates of [NiFe] Desulfovibrio gigas hydrogenase from density functional theory, INORG CHEM, 40(1), 2001, pp. 18-24
Density functional theory has been used to predict the structures of a vari
ety of active site models for the unready states, Ni-A and NI-SU, of the [N
iFe] hydrogenase from Desulfovibrio gigas. By comparing available experimen
tal results on Ni-A, Ni-SU, and Ni-SI with the computational results on the
se model complexes, we have been able to identify the most likely formulas
and structures for the active sites of W-A and NI-SU. Ni-A is predicted to
be a Ni(III)-Fe(II) species with the bridging hydroxo ligand, rather than t
he expected oxo ligand, while Ni-SU is predicted to be a Ni(II)-Fe(II) spec
ies with a water molecule coordinated to the Fe center. Both have one of th
e terminal S atoms (cysteines) protonated.