DFT calculations of the electronic structure of the paramagnetic states Ni-A, Ni-B and Ni-C of [NiFe] hydrogenase

1 January 2001

journal article
Published by Royal Society of Chemistry (RSC) in Physical Chemistry Chemical Physics

Vol. 3 (13) , 2668-2675
https://doi.org/10.1039/b101508g

Abstract

Structural parameters and atomic spin densities of the active centre of [NiFe] hydrogenases in the paramagnetic states Ni-A, Ni-B and Ni-C are reported. The DFT (BLYP/DZVP) calculated spin density distribution is found to be in good agreement with experimental data when the bridging ligand is OH⁻ in the Ni-B and O²⁻ in the Ni-A states of the enzyme. For the reduced enzyme (Ni-C) it is postulated that a hydride ligand bridges the Ni and Fe atoms. The atomic spin densities for the proposed paramagnetic states are in good agreement with experimental electron magnetic resonance data. Based on the deduced composition of the states Ni-A, Ni-B and Ni-C a model for the reaction mechanism is proposed.

Keywords

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