Cerium is unique amongst the lanthanides for having two accessible oxidation states: +3 and +4. The ability of cerium to act as a Lewis acid and undergo redox reactions has made it attractive in organic synthesis and as potential catalysts including acting as photoredox catalysts. The cerium oxidation state can be tuned by coordination of electron donating or withdrawing ligands. Electron withdrawing ligands stabilize the trivalent oxidation state whereas ligands with electron donating groups stabilize the tetravalent state. Ligands bearing bidentate oxygen donors are also known to stabilize the tetravalent state. In order to study the effects of redox tuning, the beta-diketonate ligand provides the same donor atoms and allows for fine adjustments of the electronic and steric properties of the ligand. Several beta-diketonate Ce complexes of the form Ce(beta-diketonate)3 hydrate or Ce(beta-diketonate)4 were prepared and analyzed by 1H and 13C NMR, FT-IR, DSC, cyclic voltammetry, X-ray crystallography and UV-Vis. We synthesized all Ce complexes in solution and mechanochemically to compare the results using the aforementioned techniques. The results obtained from this study will be used to design structurally related redox active bidentate oxygen donor ligands.

Synthesis and characterization of redox tunable cerium complexes containing beta-diketonate ligands

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.