Multi‐electron Oxidation of Ce(III) Complexes Facilitated by Redox‐Active Ligands
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A family of cerium complexes featuring a redox-active ligand in different oxidation states has been synthesized, including the the iminosemiquinone (isq)<sup>1−</sup> compound, Ce(<sup>dipp</sup>isq)<sub>3</sub> (1-Ceisq), and the amidophenolate (ap)<sup>2−</sup> species Ce<sup>III</sup>(<sup>dipp</sup>ap)<sub>3</sub>K<sub>3</sub> (2-Ceap), [Ce<sup>III</sup>(<sup>dipp</sup>ap)<sub>3</sub>K][K(18-c-6)]<sub>2</sub> (2-Ceap 18c6), and [Ce<sup>III</sup>(<sup>dipp</sup>ap)<sub>3</sub>K][K(15-c-5)<sub>2</sub>]<sub>2</sub> (2-Ceap 15c5). Treating 2-Ceap 15c5 with dioxogen furnishes the cerium(IV) derivative [Ce<sup>IV</sup>(<sup>dipp</sup>ap)<sub>3</sub>][K(15-c-5)<sub>2</sub>]<sub>2</sub> (3-Ceap 15c5), and an analogous synthesis can be used to generate [Ce<sup>IV</sup>(<sup>dipp</sup>ap)<sub>3</sub>][K(crypt)]<sub>2</sub> (3-Ceap crypt). Similarly, addition of hexamethyldisiloxane produces an interesting bis(amidophenolate) species, [(Me<sub>3</sub>SiO)<sub>2</sub>Ce<sup>IV</sup>(<sup>dipp</sup>ap)<sub>2</sub>][K(15-c-5)<sub>2</sub>]<sub>2</sub> (4-CeOSiMe<sub>3</sub>). In conclusion, full spectroscopic and structural characterization of each derivative was performed to establish the oxidation states of both the ligands and the cerium ions.. Authors: Rupasinghe, D. M. Ramitha Y. P. [Purdue Univ., West Lafayette, IN (United States)] (ORCID:0000000166958973); Lopez, Lauren M. [Purdue Univ., West Lafayette, IN (United States)] (ORCID:0009000730212855); Poore, Andrew T. [Purdue Univ., West Lafayette, IN (United States)] (ORCID:0009000716500471); Baxter, Makayla R. [Purdue Univ., West Lafayette, IN (United States)]; Lin, Nathan J. [Purdue Univ., West Lafayette, IN (United States)]. DOE Contract: SC0008479. Subjects: Chemistry