Reactivity of UH₃ with mild oxidants

Addition of 2 equiv of I₂ to a stirring suspension of UH₃ in Et₂O results in vigorous gas evolution and the formation of UI₄(OEt₂)₂ (1), which can be isolated in good yields as an air- and moisture-sensitive brick-red powder. Addition of 3 equiv of AgBr to UH₃ in DME produces UBr₃(DME)₂ (2), while addition of 4 equiv of AgX to UH₃ in DME–CH₂Cl₂ provides UX₄(DME)₂ (X = Br, 3; Cl, 4). Similarly, the reaction of 4 equiv of AgOTf with UH₃ in neat DME generates U(OTf)₄(DME)₂ (5). Each of these reactions proceeds with the evolution of hydrogen. Complex 1 can also be generated by reaction of 4 equiv of Me₃SiI with UCl₄ in Et₂O. All complexes were fully characterized, including analysis by X-ray crystallography.