Dinitrogen cleavage and hydrogenation to ammonia with a uranium complex

The Haber-Bosch process produces ammonia (NH₃) from dinitrogen (N₂) and dihydrogen (H₂), but requires high temperature and pressure. Before iron-based catalysts were exploited in the current industrial Haber-Bosch process, uranium-based materials served as effective catalysts for production of NH₃ from N₂. Although some molecular uranium complexes are known to be capable of combining with N₂, further hydrogenation with H₂ forming NH₃ has not been reported to date. Here, we describe the first example of N₂ cleavage and hydrogenation with H₂ to NH₃ with a molecular uranium complex. The N₂ cleavage product contains three uranium centers that are bridged by three imido μ ₂-NH ligands and one nitrido μ ₃-N ligand. Labeling experiments with ¹⁵N demonstrate that the nitrido ligand in the product originates from N₂. Reaction of the N₂-cleaved complex with H₂ or H⁺ forms NH₃ under mild conditions. A synthetic cycle has been established by the reaction of the N₂-cleaved complex with trimethylsilyl chloride. The isolation of this trinuclear imido-nitrido product implies that a multi-metallic uranium assembly plays an important role in the activation of N₂.