Homogeneous electrocatalysts are mostly based on expensive and rare metals such as Ru and Re, making it difficult to envision their use in large scale employment of systems for the synthesis of renewable chemicals and fuels from CO2.  Notably there are very few reports of electrocatalytic CO2 reduction by group 6 metals, even though this group contains metals commonly found in the active sites of formate dehydrogenase enzymes, which interconvert CO2 and formate. Thus we report the spectroscopic, photochemical and electrochemical properties of group 6 complexes including the type M(bpy-R)(CO)4 (R = H, tBu; M = Mo, W).    These complexes are found to be competent but slow catalysts for CO2 reduction through a two-electron process, generating a diamagnetic dianion complex.  Compared to the analogous group 7 catalysts, these group 6 catalysts display stronger back donation to CO, which suggests that CO binding competes with CO2 binding, contributing to slower rates.

Electrocatalytic CO<sub>2</sub> reduction by group 6 complexes

248th National Meeting (2014)

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Electrocatalytic CO2 reduction by group 6 complexes

Electrocatalytic CO₂ reduction by group 6 complexes