title: Synthesis, molecular and electronic structure of U(V)(O)[N(SiMe3)2]3.
abstract: Addition of 1 equiv of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to U(NR(2))(3) in hexanes affords U(O)(NR(2))(3) (2), which can be isolated in 73% yield. Complex 2 is a rare example of a terminal U(V) oxo complex. In contrast, addition of 1 equiv of Me(3)NO to U(NR(2))(3) (R = SiMe(3)) in pentane generates the U(IV) bridging oxo [(NR(2))(3)U](2)(μ-O) (3) in moderate yields. Also formed in this reaction, in low yield, is the U(IV) iodide complex U(I)(NR(2))(3) (4). The iodide ligand in 4 likely originates from residual NaI, present in the U(NR(2))(3) starting material. Complex 4 can be generated rationally by addition of 0.5 equiv of I(2) to a hexane solution of U(NR(2))(3), where it can be isolated in moderate yield as a tan crystalline solid. The solid-state molecular structures and magnetic susceptibilities of 2, 3, and 4 have been measured. In addition, the electronic structures of 2 and 3 have been investigated by density functional theory (DFT) methods.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, United States.
authors.forename: Skye
authors.initials: S
authors.lastname: Fortier
authors.forename: Jessie L
authors.initials: JL
authors.lastname: Brown
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