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Siloxides as Supporting Ligands in Uranium(III)-Mediated Small-Molecule Activation


  • We thank Colette Lebrun and Pierre A. Bayle for their help with spectroscopic characterization. We acknowledge support from the Commissariat à l’Energie Atomique, Direction de l’Energie Nucléaire, RBPCH program and by the “Agence Nationale de la Recherche” (ANR-10-BLAN-0729). CAlmip and Cines are acknowledged for generous grants of computing time. L.M. is a member of the Institut Universitaire de France.


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Siloxides can support U! …in the reduction of small molecules with uranium complexes. The treatment of [U{N(SiMe3)2}3] with HOSi(OtBu)3 (3 equiv) yielded a novel homoleptic uranium(III) siloxide complex 1, which acted as a two-electron reducing agent toward CS2 and CO2 (see scheme). Complex 1 also reduced toluene to afford a diuranium inverted-sandwich complex.