First-principle molecular dynamics simulation of a NiFe-hydrogenase model compound

The recent discovery of a model compounds of [NiFe] hydrogenase that catalyzes the heterolytic cleavage of the H 2 molecule into a proton and a stable hydride in water solution under room conditions opened up the possibility to understand the mechanism of H 2 uptake by this peculiar class of enzymes. The simplest model compound belongs to the class of NiRu bimetallic cationic complexes mimicking, in water solution and at room conditions, the hydrogenase active site. By using first-principles molecular dynamics computer simulations, in the Car-Parrinello scheme, we investigated models including the water solvent and nitrate counterions. Several simulations, starting from different initial configurations, provided information on the first step of the H 2 cleavage: (1) the pathway of H2 approach towards the active site; (2) the role of the ruthenium-bonded water molecule in providing a base that extracts the proton from the activated H 2 molecule; (3) the minor role of Ni in activating the H 2 molecule and its role in stabilizing the hydride produced.