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Keywords:

  • density functional calculations;
  • ENDOR spectroscopy;
  • enzyme models;
  • EPR spectroscopy;
  • hydrogenases
Thumbnail image of graphical abstract

Convincing evidence for the presence of a nitrogen atom in the dithiolate bridge of the active site of native [FeFe] hydrogenases (B) is provided by a spectroscopic, electrochemical, and theoretical study of a well-characterized structural mimic of the [FeFe] hydrogenase subcluster (picture: 14N matched-HYSCORE spectrum of the model compound A). This result should help to understand the mechanism of dihydrogen conversion and production.