Issue 22, 2022

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

Abstract

Treatment of [UIV(N3)(TrenTIPS)] (1, TrenTIPS = {N(CH2CH2NSiPri3)3}3−) with excess Li resulted in the isolation of [{UIV(μ-NLi2)(TrenTIPS)}2] (2), which exhibits a diuranium(IV) ‘diamond-core’ dinitride motif. Over-reduction of 1 produces [UIII(TrenTIPS)] (3), and together with known [{UV(μ-NLi)(TrenTIPS)}2] (4) an overall reduction sequence 1423 is proposed. Attempts to produce an odd-electron nitride from 2 resulted in the formation of [{UIV(TrenTIPS)}2(μ-NH)(μ-NLi2)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 U2N2.

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

Supplementary files

Article information

Article type
Paper
Submitted
31 mar 2022
Accepted
20 mai 2022
First published
20 mai 2022
This article is Open Access
Creative Commons BY license

Dalton Trans., 2022,51, 8855-8864

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

D. M. King, B. E. Atkinson, L. Chatelain, M. Gregson, J. A. Seed, A. J. Wooles, N. Kaltsoyannis and S. T. Liddle, Dalton Trans., 2022, 51, 8855 DOI: 10.1039/D2DT00998F

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