Plutonium(III) versus uranium(III) and samarium(III) in small molecule activation chemistry.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 42069665.
- Also identified by DOI 10.1038/s41467-026-72229-7.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
We report the Pu<sup>III</sup> complex, [Pu<sup>III</sup>(Cp<sup>Me4</sup>)<sub>3</sub>] (1-Pu), and demonstrate its differences in small molecule reactivity compared to the U<sup>III</sup> and Sm<sup>III</sup> analogs, [U<sup>III</sup>(Cp<sup>Me4</sup>)<sub>3</sub>] (1-U) and [Sm<sup>III</sup>(Cp<sup>Me4</sup>)<sub>3</sub>] (1-Sm), respectively. 1-Pu reductively cleaves the small molecule (PhS)<sub>2</sub>, affording a Pu<sup>III</sup> complex, [{Pu<sup>III</sup>(Cp<sup>Me4</sup>)<sub>2</sub>}<sub>2</sub>(μ-SPh)<sub>2</sub>] (2-Pu), while retaining the Pu<sup>III</sup> center and eliminating (Cp<sup>Me4</sup>)<sub>2</sub> as a by-product, a fingerprint of a sterically induced reduction (SIR) reaction. Sm is often used as a surrogate for Pu, but the analogous [Sm<sup>III</sup>(Cp<sup>Me4</sup>)<sub>3</sub>], (1-Sm), is unreactive. The (PhS)<sub>2</sub> cleavage by 1-U proceeds solely via a metal-based oxidation (i.e., U<sup>III</sup> → U<sup>IV</sup>), to form [U<sup>IV</sup>(Cp<sup>Me4</sup>)<sub>3</sub>(SPh)] (3-U). Only 1-U reacts with (PhHN)<sub>2</sub>, affording the reductive cleavage product, [U<sup>IV</sup>(Cp<sup>Me4</sup>)<sub>3</sub>(NHPh)] (4-U). The difference in reactivity of 1-Pu compared to complexes 1-Sm and 1-U was unexpected, and since SIR chemistry can enable complexes to participate in otherwise impossible reductive transformation of substrates, this reinforces the importance of studying small molecule reactivity with the transuranic elements.