Modeling the active sites of metalloenzymes. 4. Predictions of the unreadystates of [NiFe] Desulfovibrio gigas hydrogenase from density functional theory

Authors
Citation
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
Citations number
39
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
INORGANIC CHEMISTRY
ISSN journal
00201669 → ACNP
Volume
40
Issue
1
Year of publication
2001
Pages
18 - 24
Database
ISI
SICI code
0020-1669(20010101)40:1<18:MTASOM>2.0.ZU;2-I
Abstract
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.