The electronic structure of the catalytic intermediate Ni-C in [NiFe] and [NiFeSe] hydrogenasesElectronic Supplementary Information available. See http://www.rsc.org/suppdata/cp/b1/b105723p/
- 21 November 2001
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Physical Chemistry Chemical Physics
- Vol. 3 (23) , 5115-5120
- https://doi.org/10.1039/b105723p
Abstract
The catalytic intermediate Ni-C in the heterolytic cleavage of molecular hydrogen is studied using relativistic DFT calculations. The difference between the [NiFe] and [NiFeSe] hydrogenases is investigated and it is found that structural modifications lead to changes in the electronic structure, manifested by g-values and hyperfine interactions. The sulfur to selenium substitution leads to small changes in the structural parameters and the spin density distribution. The g-tensor principal values are changed but the g-tensor orientation is retained in both enzymes. The hyperfine parameters show small but systematic changes. Participation of the terminal cysteine Cys530 in the reaction mechanism is discussed.Keywords
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