B03 - Metalloenzymes, Bioinspired Complexes and Hybrids for H2 Activation

Reversible H2/H+ interconversion in hydrogenases (eq. 1) represents the most fundamental of all multi-PCET processes. Understanding how these enzymes operate at close to zero overpotential requires in-depth mechanistic insights for the protein active sites, which then informs the bioinspired design of new and efficient H2 evolution/splitting catalysts. In a combined analytical and synthetic approach, project B03 aims at elucidating details of the PCET scenario in [Fe]- and [NiFe]-hydrogenases and synthetic analogues using new NMR tools, and at developing biomimetic NiFe complexes that exploit thiolato ligands and second sphere effects for the synchronization of the sequential 2H+/2e− transfer.