Revisiting the reaction mechanism of carbon monoxide dehydrogenase, a key enzyme in anaerobic carbon metabolism – COMEC

NiFe-Carbon monoxide dehydrogenase (CODH) is a complex oxygen-sensitive multi-metallic enzyme playing a key role in carbon metabolism in anaerobic microorganisms. Its active site, consisting of a heteronuclear NiFe4S4 cluster (known as the C-cluster) is unique in biology. The high efficiency of the enzyme for CO/CO2 interconversion makes it a great source of inspiration for the design of catalysts in sustainable CO2 recovery strategies. However, a deep understanding of its functioning at the molecular level is still lacking. Numerous controversies are found in the literature about key reaction intermediates and some mechanistic steps remain unclear. With the COMEC project, we intend to combine in solution (advanced EPR and XAS), in cristallo (time-resolved crystallography) and in silico (advanced QM/MM) methods on two CODH models to revisit the reaction mechanism of CODH and characterize reaction intermediates still unknown today. This challenging project will open up new synthesis strategies in bio-inspired chemistry and in catalysis for sustainable chemistry.