Facile Dinitrogen and Dioxygen Cleavage by a Uranium(III) Complex: Cooperativity Between the Non‐Innocent Ligand and the Uranium Center

Activation of dinitrogen (N₂, 78 %) and dioxygen (O₂, 21 %) has fascinated chemists and biochemists for decades. The industrial conversion of N₂ into ammonia requires extremely high temperatures and pressures. Herein we report the first example of N₂ and O₂ cleavage by a uranium complex, N(CH₂CH₂NPⁱPr₂)₃U]₂(TMEDA), under ambient conditions without an external reducing agent. The N₂ triple bond breaking implies a U^III–P^III six‐electron reduction. The hydrolysis of the N₂ reduction product allows the formation of ammonia or nitrogen‐containing organic compounds. The interaction between U^III and P^III in this molecule allows an eight‐electron reduction of two O₂ molecules. This study establishes that the combination of uranium and a low‐valent nonmetal is a promising strategy to achieve a full N₂ and O₂ cleavage under ambient conditions, which may aid the design of new systems for small molecules activation.