Two‐Electron Oxidative Atom and Group Transfer Reactions at a Well‐Defined Uranium(II) Center.

The multi‐electron redox chemistry of uranium(II) compounds remains largely unexplored. Herein, we report a series of two‐electron oxidative atom and group transfer reactions at a well‐defined uranium(II) center. The reactions of uranium(II) complexes [M][(AdTPBN3)U] (M=K(2,2,2‐cryptand) and K(18‐crown‐6)(THF)) with pyridine‐N‐oxide or nitrosobenzene, elemental sulfur/selenium or triphenylphosphine sulfide/selenide, and ditellurium salt led to the isolation of uranium(IV) terminal oxo and chalcogenido complexes [M][(AdTPBN3)UX] (X=O, S, Se, Te). In addition, the reactions of [M][(AdTPBN3)U] with aryl azides ArN3 or diazoalkanes R2CN2 quantitatively yielded uranium(IV) terminal imido [M][(AdTPBN3)UNAr] or hydrazonido(2−) complexes [M][(AdTPBN3)UN2CR2], respectively. Notably, the low‐temperature reaction between [M][(AdTPBN3)U] and mesityl azide allowed the isolation of the first uranium(IV) aryldiazenylimido complex as an intermediate. These uranium(IV)−element multiply bound compounds were fully characterized by X‐ray crystallography, 1H NMR spectroscopy, absorption spectroscopy, solution and solid‐state magnetometry, and elemental analysis. The controlled two‐electron oxidative reactions at a uranium(II) center not only expand the redox reactivity of uranium(II) but also offer a convenient new route to access uranium−element multiply bound compounds. [ABSTRACT FROM AUTHOR]