Synthesis, Electrochemistry, and Reactivity of the Actinide Trisulfides [K(18-crown-6)][An(η<sup>3</sup>‑S<sub>3</sub>)(NR<sub>2</sub>)<sub>3</sub>] (An = U, Th; R = SiMe<sub>3</sub>)
- Danil E. Smiles (1705384)
- Guang Wu (28409)
- Trevor W. Hayton (1409836)
DOIAbstract
The reaction of [Th(I)(NR<sub>2</sub>)<sub>3</sub>] (R = SiMe<sub>3</sub>) with [K(18-crown-6)]<sub>2</sub>[S<sub>4</sub>] results in the formation of [K(18-crown-6)][Th(η<sup>3</sup>-S<sub>3</sub>)(NR<sub>2</sub>)<sub>3</sub>] (<b>2</b>). Oxidation of <b>2</b>, or its uranium analogue, [K(18-crown-6)][U(η<sup>3</sup>-S<sub>3</sub>)(NR<sub>2</sub>)<sub>3</sub>] (<b>1</b>), with AgOTf, in an attempt to generate an [S<sub>3</sub>]<sup>•–</sup> complex, results in the formation of [K(18-crown-6)][An(OTf)<sub>2</sub>(NR<sub>2</sub>)<sub>3</sub>] (<b>3</b>, An = U; <b>4</b>, An = Th) as the only isolable products. These results suggest that the putative [S<sub>3</sub>]<sup>•–</sup> ligand is only weakly coordinating and can be easi...
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