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Journal Articles Journal of the American Chemical Society Year : 2019

A Uranium Tri-Rhenium Triple Inverse Sandwich Compound

Trevor D. Lohrey
  • Function : Author
Guodong Rao
  • Function : Author
R. David Britt
  • Function : Author

Abstract

Salt metathesis between the anionic rhenium(I) compound, Na[Re(eta(5)-Cp)(BDI)] (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-beta-diketiminate), and the uranium(III) salt, UI3 (1,4-dioxane)(1.5), generated the triple inverse sandwich complex, U[(mu-eta(5):eta(5)-Cp)Re(BDI)(3), which was isolated and structurally characterized as the Lewis base adducts, (L)U[(mu-eta(5):eta(5)-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(eta(5)-Cp)(BDI)] was observed in the solid-state and reproduced in calculated structures of 1-THF and the anionic fragment, [Re(eta(5)-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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Dates and versions

hal-04022182 , version 1 (09-03-2023)

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Michael A. Boreen, Trevor D. Lohrey, Guodong Rao, R. David Britt, Laurent Maron, et al.. A Uranium Tri-Rhenium Triple Inverse Sandwich Compound. Journal of the American Chemical Society, 2019, 141 (13), pp.5144-5148. ⟨10.1021/jacs.9b01331⟩. ⟨hal-04022182⟩
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