MPA Division, Los Alamos National Laboratory, MS J514, Los Alamos, New Mexico 87545, USA.
Inorg Chem. 2011 May 16;50(10):4235-7. doi: 10.1021/ic200377b. Epub 2011 Apr 8.
The conproportionation reaction between the dimeric diimidouranium(V) species U(N(t)Bu)(2)(I)((t)Bu(2)bpy) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) and UI(3)(THF)(4) in the presence of additional (t)Bu(2)bpy yields U(N(t)Bu)(I)(2)((t)Bu(2)bpy)(THF)(2) (2), an unprecedented example of a monoimidouranium(IV) dihalide complex. The general synthesis of this family of uranium(IV) derivatives can be achieved more readily by adding 2 equiv of MN(H)R (M = Li, K; R = (t)Bu, 2,6-(i)PrC(6)H(3), 2-(t)BuC(6)H(4)) to UX(4) in the presence of coordinating Lewis bases to give complexes with the general formula U(NR)(X)(2)(L)(n) (X = Cl, I; L = (t)Bu(2)bpy, n = 1; L = THF, n = 2). The complexes were characterized by (1)H NMR spectroscopy and single-crystal X-ray diffraction analysis of compounds 2 and {UN(2,6-(i)PrC(6)H(3))(2)(THF)(2)}(2) (4). (The X-ray structures of 5 and 6 are reported in the Supporting Information.)
二聚二咪唑鎓(V)物种U(N(t)Bu)(2)(I)((t)Bu(2)bpy) ((t)Bu(2)bpy = 4,4'-二-叔丁基-2,2'-联吡啶)与 UI(3)(THF)(4)在额外(t)Bu(2)bpy 的存在下发生比例反应，生成 U(N(t)Bu)(I)(2)((t)Bu(2)bpy)(THF)(2) (2)，这是单咪唑鎓(IV)二卤化物配合物的空前实例。通过向 UX(4)中添加 2 当量的 MN(H)R (M = Li, K; R = (t)Bu, 2,6-(i)PrC(6)H(3), 2-(t)BuC(6)H(4))，并在配位路易斯碱的存在下，更容易实现这一系列铀(IV)衍生物的一般合成，得到通式为 U(NR)(X)(2)(L)(n) (X = Cl, I; L = (t)Bu(2)bpy, n = 1; L = THF, n = 2)的配合物。通过(1)H NMR 光谱和化合物 2 和{UN(2,6-(i)PrC(6)H(3))(2)(THF)(2)}(2) (4)的单晶 X 射线衍射分析对配合物进行了表征。(5 和 6 的 X 射线结构在支持信息中报告。)
