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A Uranium Tri-Rhenium Triple Inverse Sandwich Compound

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NIAID Data Ecosystem2026-03-11 收录
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https://figshare.com/articles/dataset/A_Uranium_Tri-Rhenium_Triple_Inverse_Sandwich_Compound/7868894
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Salt metathesis between the anionic rhenium­(I) compound, Na­[Re­(η5-Cp)­(BDI)] (BDI = N,N′-bis­(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate), and the uranium­(III) salt, UI3(1,4-dioxane)1.5, generated the triple inverse sandwich complex, U­[(μ-η5:η5-Cp)­Re­(BDI)]3, which was isolated and structurally characterized as the Lewis base adducts, (L)­U­[(μ-η5:η5-Cp)­Re­(BDI)]3 (1·L, L = THF, 1,4-dioxane, DMAP). The assignment as one uranium­(III) and three rhenium­(I) centers was supported by X-ray crystallography, NMR and EPR spectroscopies, and computational studies. An unusual shortening of the rhenium–Cp bond distances in 1·L relative to Na­[Re­(η5-Cp)­(BDI)] was observed in the solid-state and reproduced in calculated structures of 1·THF and the anionic fragment, [Re­(η5-Cp)­(BDI)]−. Calculations suggest that the electropositive uranium center pulls electron density away from the electron-rich rhenium centers, reducing electron–electron repulsions in the rhenium–Cp moieties and thereby strengthening those interactions, while also making uranium–Cp bonding more favorable.
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2019-03-20
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