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Hydrogenases: Theoretical Investigations Towards Bioinspired H2 Production and Activation

  1. Maurizio Bruschi,
  2. Giuseppe Zampella,
  3. Claudio Greco,
  4. Luca Bertini,
  5. Piercarlo Fantucci,
  6. Luca De Gioia

Published Online: 15 SEP 2009

DOI: 10.1002/0470862106.ia624

Encyclopedia of Inorganic Chemistry

Encyclopedia of Inorganic Chemistry

How to Cite

Bruschi, M., Zampella, G., Greco, C., Bertini, L., Fantucci, P. and De Gioia, L. 2009. Hydrogenases: Theoretical Investigations Towards Bioinspired H2 Production and Activation. Encyclopedia of Inorganic Chemistry. .

Author Information

  1. University of Milano-Bicocca, Milano, Italy

Publication History

  1. Published Online: 15 SEP 2009


Hydrogenases catalyze the reduction of protons, and have great biotechnological relevance in light of the key role played by H2 in several industrial processes. Moreover, the industrial and social relevance of H2 stems also from the observation that dihydrogen could be an efficient and cost-attractive energy carrier for the future.

Hydrogenases invariably contain a transition metal ion (Fe and in some case Ni) in their active site, and therefore have attracted the attention of experimental and theoretical bioinorganic chemists, which have given fundamental contributions to the elucidation of structure-activity relationships in this class of enzymes. In addition, the recent elucidation of the X-ray structure of [NiFe]- and [FeFe]-hydrogenases has prompted synthetic chemists to design and characterize bioinspired coordination compounds, with the aim of obtaining efficient catalysts for H2 production/activation.

Here, we briefly review the contributions given by quantum chemistry to the characterization of key forms of the enzymes, the elucidation of reaction pathways and catalytic mechanisms, as well as the complementation of experimental data in the investigation of synthetic models. Emphasis is mainly given to underline the kind of insights that can be obtained using quantum chemical methods when investigating coordination compounds related to the hydrogenases active site, and to highlight some strengths and limitations of density functional theory, which currently is the most frequently used quantum chemical method to investigate metalloenzymes.


  • hydrogen;
  • density functional theory;
  • bioinorganic chemistry;
  • enzymes;
  • iron;
  • nickel;
  • quantum chemistry;
  • catalysis