Multimetallic cooperativity in uranium-mediated CO₂ activation

Area of Science:

• Organometallic chemistry
• f-element chemistry
• Catalysis

Background:

• Metal-mediated carbon dioxide (CO2) transformation under mild conditions is crucial.
• Cooperativity between metal and Lewis acid centers is key for small-molecule activation.
• This cooperative effect has not been explored for f-elements.

Purpose of the Study:

• Investigate the cooperative effect in f-element complexes for CO2 reduction.
• Explore the role of potassium in uranium complexes for CO2 activation.
• Understand the redox transformations of CO2 mediated by U-K systems.

Main Methods:

• Synthesis of potassium-containing uranium complexes with sterically demanding ligands.
• Study of CO2 transformation reactions using these complexes.
• Density Functional Theory (DFT) calculations to elucidate reaction mechanisms.

Main Results:

• A U, K complex promoted selective reductive disproportionation of CO2 to CO.
• A heterobimetallic U-K complex facilitated potassium-assisted two-electron reductive cleavage of CO2 to CO.
• Observation of a U(V) terminal oxo complex, showcasing two-electron transfer in U(III) chemistry.

Conclusions:

• The presence of potassium in uranium complexes induces significant cooperative effects in CO2 reduction.
• These f-element systems offer novel pathways for CO2 transformation under mild conditions.
• DFT studies confirm the cooperative role of uranium and potassium centers in CO2 activation.