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Probing the reactivity and electronic structure of a uranium(V) terminal oxo complex
Skye Fortier1, Nikolas Kaltsoyannis, Guang Wu
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
Abstract:
Treatment of the U(III)-ylide adduct U(CH(2)PPh(3))(NR(2))(3) (1, R = SiMe(3)) with TEMPO generates the U(V) oxo metallacycle [Ph(3)PCH(3)][U(O)(CH(2)SiMe(2)NSiMe(3))(NR(2))(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)(CH(2)SiMe(2)NSiMe(3))(NR(2))(2) (3). The electronic structures of 2 and 3 are investigated by DFT analysis. Additionally, the nucleophilicity of the oxo ligands in 2 and 3 toward Me(3)SiI is explored.
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