Oxidative Addition of E‐H (E = C, N) Bonds to Transient Uranium(II) Centers

Abstract

Two‐electron oxidative addition is one of the most important elementary reactions for d‐block transition metals but it is uncommon for f‐block elements. Here, we report the first examples of intermolecular oxidative addition of E‐H (E = C, N) bonds to uranium(II) centers. The transient U(II) species was formed in‐situ by reducing a heterometallic cluster featuring U(IV)‐Pd(0) bonds with potassium‐graphite (KC8). Oxidative addition of C‐H or N‐H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1‐adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N2O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two‐ or four‐electron processes. This study demonstrates that the intermolecular two‐electron oxidative addition reactions are viable for actinide elements.