Journal of the American Chemical Society, Vol.133, No.36, 14224-14227, 2011
Probing the Reactivity and Electronic Structure of a Uranium(V) Terminal Oxo Complex
Treatment of the U(III)-ylide adduct U-(CH2PPh3)(NR2)(3) (1, R = SiMe3) with TEMPO generates the U(V) oxo metallacycle [Ph3PCH3][U(O)(CH2SiMe2-NSiMe3)(NR2)(2)] (2) via O-atom transfer, in good yield. Oxidation of 2 with 0.85 equiv of AgOTf affords the neutral U(VI) species U(O)(CH2SiMe2NSiMe3)(NR2)(2) (3). The electronic structures of 2 and 3 are investigated by DFT analysis. Additionally, the nudeophilicity of the oxo ligands in 2 and 3 toward Me3SiI is explored.