Early Transition Metal Metallocenes for the Electrochemical Reduction of Carbon Monoxide

The electroreduction of carbon monoxide (COR) to highly reduced carbon products is an attractive method to supplement thermal Fischer-Tropsch processes, which have poor selectivity and significant infrastructural requirements. Importantly, when coupled to the electrocatalytic reduction of carbon dioxide (CO2R), COR is a promising method to transform the greenhouse gas CO2 to value-added products using electricity generated from sustainable energy sources. To this point, no molecular electrocatalyst capable of efficiently realizing COR under ambient conditions has been reported, motivating us to test promising organometallic frameworks. To this end, metallocenes featuring two cyclopentadienyl groups ligated to a group IV to VI transition metal centers were investigated in this work. Their electrochemical properties were characterized, their ability to serve as a precatalyst for COR was examined, and their interaction with carbon monoxide at reducing potentials was studied. Initial results suggest that metallocene dichlorides have the potential to work as the precatalysts for COR to CH4. In the future, this framework will need to be modified in order to improve its selectivity and stability.