The complex [BrMn(bpy)(CO)3] is an established electrocatalyst effecting the reduction of CO2 to CO. However, it suffers from facile photochemical decomposition, making it impractical to employ as a homogeneous catalyst. While we have demonstrated several modifications of this complex that help to mitigate this decomposition route, these variations have not provided a sufficient degree of stability to produce a functional electrocatalyst. We now report that the cyanide-bridged dimer shown in the Figure, {[Mn(bpy)(CO)3]2(m-CN)}+, eliminates the deleterious photochemistry. Further, this cyanide-bridged dimer is not only a viable electrocatalyst but is effective as a photocatalyst for the reduction of CO2 to CO when irradiated into the metal to bpy charge transfer band. Carbon dioxide reduction involves the initial photodissociation of a CO ligand providing a site for CO2 binding. Follow up photochemically induced processes lead to the reduction of the bound CO2 ligand. The photochemical reduction of CO2 appears to follow the electrochemical reduction of CO2 using this complex.

Photocatalyst for the conversion of CO2 to CO based on the [XMnbpy(CO)3] system

256th National Meeting (2018)

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