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Abstract Converting CO₂into industrially useful products is an appealing strategy for utilization of an abundant chemical resource. Electrochemical CO₂reduction (eCO₂R) offers a pathway to convert CO₂into CO and ethylene, using renewable electricity. These products can be efficiently copolymerized by organometallic catalysts to generate polyketones. However, the conditions for these reactions are very different, presenting the challenge of coupling microenvironments typically encountered for the transformation of CO₂into highly complex but desirable multicarbon products. Herein, we present a system to produce polyketone plastics entirely derived from CO₂and water, where both the CO and C₂H₄intermediates are produced by eCO₂R. In this system, a combination of Cu and Ag gas diffusion electrodes is used to generate a gas mixture with nearly equal concentrations of CO and C₂H₄, and a recirculatory CO₂reduction loop is used to reach concentrations of above 11% each, leading to a current‐to‐polymer efficiency of up to 51% and CO₂utilization of 14%. 

Samarium diiodide (SmI₂) is a privileged, single-electron reductant deployed in diverse synthetic settings. However, generalizable methods for catalytic turnover remain elusive because of the well-known challenge associated with cleaving strong Sm^III–O bonds. Prior efforts have focused on the use of highly reactive oxophiles to enable catalyst turnover. However, such approaches give rise to complex catalyst speciation and intrinsically limit the synthetic scope. Herein, we leveraged a mild and selective protonolysis strategy to achieve samarium-catalyzed, intermolecular reductive cross-coupling of ketones and acrylates with broad scope. The modularity of our approach allows rational control of selectivity based on solvent, pK_a(whereK_ais the acid dissociation constant), and the samarium coordination sphere and provides a basis for future developments in catalytic and electrocatalytic lanthanide chemistry.