Comparison of the redox chemistry of primary and secondary amides of U(IV): isolation of a U(VI) bis(imido) complex or a homoleptic U(VI) amido complex.

摘要: Reaction of UCl4 with 6 equiv LiNHtBu generates the U(IV) homoleptic amide complex [Li(THF)2Cl]2[Li]2[U(NHtBu)6] (1·THF) in 57% yield. In solid-state, 1·THF exists as a one-dimensional coordination polymer consisting alternating [Li]2[U(NHtBu)6] and [Li(THF)2Cl]2 building blocks. Recrystallization from DME/hexanes affords monomeric DME derivative, [Li(DME)2ClLi]2[U(NHtBu)6] (1·DME), which was also characterized by X-ray crystallography. The oxidation 1 AgOTF U(VI) bis(imido) [Li(THF)]2[U(NtBu)2(NHtBu)4] (2) low contrast, I2, presence excess tert-butylamine, cleanly U(NtBu)2(NHtBu)2(NH2tBu)2 (3) 78% We have explored reactivity lithium salt secondary amide. Thus, reaction (LiNC5H10) (HNC5H10 = piperidine) produces amide, [Li(DME)][U(NC5H10)5] (4). Oxidation this material ...