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American Chemical Society, Journal of the American Chemical Society, 36(133), p. 14224-14227

DOI: 10.1021/ja206083p

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Probing the Reactivity and Electronic Structure of a Uranium(V) Terminal Oxo Complex

Journal article published in 2011 by Skye Fortier, Nikolas Kaltsoyannis ORCID, Guang Wu, Tw Hayton
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

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.