The protonation of the FeFe and NiFe sites of the hydrogenases is a critical step in the formation of dihydrogen by these enzymes and their models.  The details by which protons attack the metal remain puzzling since protonation of models is known to occur at M-M bonds as well as at individual metal centers depending on the coligands. It is also known from the work of Norton that protonation of low valent metals is generally slow, which contrasts with the high rates of hydrogen evolution catalyzed by these enzymes. Using NMR spectroscopy and exploiting some new model complexes, we will discuss new ideas and new evidence for how protons attack the dimetal centers.

Pathways for protonation of metal thiolates related to the active sites of the hydrogenases

244th National Meeting (2012)

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