Deprotonation of [U(TrenTIPS)(NH2)] (1) [TrenTIPS = N(CH2CH2NSiPri3)3] with organoalkali metal reagents MR (M = Li, R = But; M = Na鈥揅s, R = CH2C6H5) afforded the imido-bridged dimers [{U(TrenTIPS)(渭-N[H]M)}2] [M = Li鈥揅s (2a鈥?b>e)]. Treatment of 2c (M = K) with 2 equiv of 15-crown-5 ether (15C5) afforded the uranium terminal parent imido complex [U(TrenTIPS)(NH)][K(15C5)2] (3c), which can also be viewed as a masked uranium(IV) nitride. The uranium鈥搃mido linkage was found to be essentially linear, and theoretical calculations suggested 蟽2蟺4 polarized U鈥揘 multiple bonding. Attempts to oxidize 3c to afford the neutral uranium terminal parent imido complex [U(TrenTIPS)(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium鈥搉itride complex [U(TrenTIPS)(N)] (5); this reaction is a new way to prepare the terminal uranium鈥搉itride linkage and was calculated to be exothermic by 鈭?.25 kcal mol鈥?.
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