Uranium–nitride chemistry: uranium–uranium electronic communication mediated by nitride bridges

Treatment of [U(IV)(N(3))(Tren(TIPS))] (1, Tren(TIPS) = {N(CH(2)CH(2)NSiPr(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(2)N(2).