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<p>We report the Pu<sup>III</sup> complex, [Pu<sup>III</sup>(Cp<sup>Me4</sup>)<sub>3</sub>] (<b>1-Pu</b>), 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>] (<b>1-U</b>) and [Sm<sup>III</sup>(Cp<sup>Me4</sup>)<sub>3</sub>] (<b>1-Sm</b>), respectively. <b>1-Pu</b> 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>(<i>μ</i>-SPh)<sub>2</sub>] (<b>2-Pu</b>), 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>], (<b>1-Sm</b>), is unreactive. The (PhS)<sub>2</sub> cleavage by <b>1-U</b> 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)] (<b>3-U</b>). Only <b>1-U</b> reacts with (PhHN)<sub>2</sub>, affording the reductive cleavage product, [U<sup>IV</sup>(Cp<sup>Me4</sup>)<sub>3</sub>(NHPh)] (<b>4-U</b>). The difference in reactivity of <b>1-Pu</b> compared to complexes <b>1-Sm</b> and <b>1-U</b> 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.</p>

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Plutonium(III) versus uranium(III) and samarium(III) in small molecule activation chemistry

  • 期刊论文

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  • 发表日期：

    2026年5月2日

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  • Megan Keener,
  • Thayalan Rajeshkumar,
  • Cambell S. Conour,
  • Joshua J. Woods,
  • Laurent Maron,
  • Polly L. Arnold

摘要

We report the PuIII complex, [PuIII(CpMe4)3] (1-Pu), and demonstrate its differences in small molecule reactivity compared to the UIII and SmIII analogs, [UIII(CpMe4)3] (1-U) and [SmIII(CpMe4)3] (1-Sm), respectively. 1-Pu reductively cleaves the small molecule (PhS)2, affording a PuIII complex, [{PuIII(CpMe4)2}2(μ-SPh)2] (2-Pu), while retaining the PuIII center and eliminating (CpMe4)2 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 [SmIII(CpMe4)3], (1-Sm), is unreactive. The (PhS)2 cleavage by 1-U proceeds solely via a metal-based oxidation (i.e., UIII → UIV), to form [UIV(CpMe4)3(SPh)] (3-U). Only 1-U reacts with (PhHN)2, affording the reductive cleavage product, [UIV(CpMe4)3(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.