Synthesis of a nitrido-substituted analogue of the uranyl ion, [N=U=O]+.

Addition of 0.5 equiv of NaN(3) to U[NR(2)](3) (R = SiMe(3)) affords the metallacycle [Na(DME)(2)(TMEDA)][(NR(2))(2)U(mu-N)(CH(2)SiMe(2)NR)U(NR(2))(2)] (1) in 69% yield. Complex 1 is readily oxidized by 0.5 equiv of I(2), generating the mixed valent U(IV/V) nitrido complex (NR(2))(2)U(mu-N)(CH(2)SiMe(2)NR)U(NR(2))(2) (2). Alternatively, oxidation of 1 with 1 equiv of Me(3)NO affords the oxo-nitrido complex [Na(DME)(2)][(NR(2))(2)(O)U(mu-N)(CH(2)SiMe(2)NR)U(NR(2))(2)] (3) in good yield. The solid-state molecular structures of 1-3 have been determined by X-ray crystallography. A notable feature of these complexes are the inequivalent U=N-U bonding interactions. Moreover, 3 contains a trans oxo-nitrido [O=U=N](+) moiety with metrical parameters approximating those of the uranyl cation, UO(2)(2+). The magnetic properties of 1-3 were investigated by SQUID magnetometry.

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