Modeling the Active Sites of Metalloenzymes. 4. Predictions of the Unready States of [NiFe] Desulfovibrio gigas Hydrogenase from Density Functional Theory
- 7 December 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 40 (1) , 18-24
- https://doi.org/10.1021/ic0001715
Abstract
Density functional theory has been used to predict the structures of a variety of active site models for the unready states, Ni-A and Ni-SU, of the [NiFe] hydrogenase from Desulfovibrio gigas. By comparing available experimental results on Ni-A, Ni-SU, and Ni-SI with the computational results on these model complexes, we have been able to identify the most likely formulas and structures for the active sites of Ni-A and Ni-SU. Ni-A is predicted to be a Ni(III)−Fe(II) species with the bridging hydroxo ligand, rather than the expected oxo ligand, while Ni-SU is predicted to be a Ni(II)−Fe(II) species with a water molecule coordinated to the Fe center. Both have one of the terminal S atoms (cysteines) protonated.Keywords
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