Synthesis and characterization of an f-block terminal parent imido [U═NH] complex: a masked uranium(IV) nitride.

Deprotonation of [U(Tren(TIPS))(NH2)] (1) [Tren(TIPS) = N(CH2CH2NSiPr(i)3)3] with organoalkali metal reagents MR (M = Li, R = Bu(t); M = Na-Cs, R = CH2C6H5) afforded the imido-bridged dimers [{U(Tren(TIPS))(μ-N[H]M)}2] [M = Li-Cs (2a-e)]. Treatment of 2c (M = K) with 2 equiv of 15-crown-5 ether (15C5) afforded the uranium terminal parent imido complex [U(Tren(TIPS))(NH)][K(15C5)2] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium-imido linkage was found to be essentially linear, and theoretical calculations suggested σ(2)π(4) polarized U-N multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(Tren(TIPS))(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium-nitride complex [U(Tren(TIPS))(N)] (5); this reaction is a new way to prepare the terminal uranium-nitride linkage and was calculated to be exothermic by -3.25 kcal mol(-1).