Uranium-Nitride Chemistry: Uranium-Uranium Electronic Communication Mediated by Nitride Bridges

Treatment of [U ^IV(N ₃)(Tren ^TIPS)] (1, Tren ^TIPS = {N(CH ₂CH ₂NSiPr ⁱ ₃) ₃} ³⁻) with excess Li resulted in the isolation of [{U ^IV(μ-NLi ₂)(Tren ^TIPS)} ₂] (2), which exhibits a diuranium(iv) ‘diamond-core’ dinitride motif. Over-reduction of 1 produces [U ^III(Tren ^TIPS)] (3), and together with known [{U ^V(μ-NLi)(Tren ^TIPS)} ₂] (4) an overall reduction sequence 1 → 4 → 2 → 3 is proposed. Attempts to produce an odd-electron nitride from 2 resulted in the formation of [{U ^IV(Tren ^TIPS)} ₂(μ-NH)(μ-NLi ₂)Li] (5). Use of heavier alkali metals did not result in the formation of analogues of 2, emphasising the role of the high charge-to-radius-ratio of lithium stabilising the charge build up at the nitride. Variable-temperature magnetic data for 2 and 5 reveal large low-temperature magnetic moments, suggesting doubly degenerate ground states, where the effective symmetry of the strong crystal field of the nitride dominates over the spin-orbit coupled nature of the ground multiplet of uranium(iv). Spin Hamiltonian modelling of the magnetic data for 2 and 5 suggest U⋯U anti-ferromagnetic coupling of −4.1 and −3.4 cm ⁻¹, respectively. The nature of the U⋯U electronic communication was probed computationally, revealing a borderline case where the prospect of direct uranium-uranium bonding was raised, but in-depth computational analysis reveals that if any uranium-uranium bonding is present it is weak, and instead the nitride centres dominate the mediation of U⋯U electronic communication. This highlights the importance of obtaining high-level ab initio insight when probing potential actinide-actinide electronic communication and bonding in weakly coupled systems. The computational analysis highlights analogies between the ‘diamond-core’ dinitride of 2 and matrix-isolated binary U ₂N ₂