Synthesis and Characterization of an f-Block Terminal Parent Imido [U鈺怤H] Complex: A Masked Uranium(IV) Nitride

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• 作者：David M. King ; Jonathan McMaster ; Floriana Tuna ; Eric J. L. McInnes ; William Lewis ; Alexander J. Blake ; Stephen T. Liddle
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：April 16, 2014
• 年：2014
• 卷：136
• 期：15
• 页码：5619-5622
• 全文大小：256K
• 年卷期：v.136,no.15(April 16, 2014)
• ISSN：1520-5126

文摘

Deprotonation of [U(Tren^TIPS)(NH₂)] (1) [Tren^TIPS = N(CH₂CH₂NSiPrⁱ₃)₃] with organoalkali metal reagents MR (M = Li, R = Bu^t; M = Na鈥揅s, R = CH₂C₆H₅) afforded the imido-bridged dimers [{U(Tren^TIPS)(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(Tren^TIPS)(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(Tren^TIPS)(NH)] (4) resulted in spontaneous disproportionation to give 1 and the uranium鈥搉itride complex [U(Tren^TIPS)(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?.