title: Probing the reactivity and electronic structure of a uranium(V) terminal oxo complex.
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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
authors.forename: Skye
authors.initials: S
authors.lastname: Fortier
authors.forename: Nikolas
authors.initials: N
authors.lastname: Kaltsoyannis
authors.forename: Guang
authors.initials: G
authors.lastname: Wu
authors.forename: Trevor W
authors.initials: TW
authors.lastname: Hayton