Four-electron oxidation and one-electron reduction of the bis(terphenylthiolate) U(<scp>ii</scp>) complex, U(SAr<sup>iPr6</sup>)<sub>2</sub> [Ar<sup>iPr6</sup> = C<sub>6</sub>H<sub>3</sub>-2,6-(C<sub>6</sub>H<sub>2</sub>-2,4,6-<sup>i</sup>Pr<sub>3</s
The utility of the sterically bulky terphenylthiolate ligand, (SAr<sup>iPr6</sup>)<sup>1-</sup> in expanding uranium reductive chemistry has been explored. Reduction of U(SAr<sup>iPr6</sup>)<sub>2</sub>I forms the U(II) complex, U(SAr<sup>iPr6</sup>)<sub>2</sub>, in which the metal is protected by the flanking arene rings of the ligand, but they move out of the way to accommodate the four electron reduction of PhNNPh to form the U(VI) bis(imido) product U(SAr<sup>iPr6</sup>)<sub>2</sub>(NPh)<sub>2</sub>(THF)<sub>2</sub>. The KC<sub>8</sub> reduction of U(SAr<sup>iPr6</sup>)<sub>2</sub> generates a more reduced complex, KU(μ-SAr<sup>iPr6</sup>)<sub>2</sub>, initially identified by a -2.55 V <i>vs.</i> Fc<sup>+</sup>/Fc electrochemical reduction event in THF.
Authors
- Joseph W. Ziller (ORCID: https://orcid.org/0000-0001-7404-950X)
- Ahmadreza Rajabi
- Filipp Furche
- Joshua D. Queen
- William J. Evans (ORCID: https://orcid.org/0000-0002-0651-418X)
- Ernest Ma (ORCID: https://orcid.org/0000-0002-3986-1348)
Institutions
- University of California, Irvine (US)
- Irvine University (US)
Publication Details
- Journal
- Chemical Communications
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5cc02284c
- Citations
- 2
- Primary Topic
- Radioactive element chemistry and processing
- Type
- article
- Field-Weighted Citation Impact
- 1.07