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

被引：108
作者：
King, David M. [1 ]
McMaster, Jonathan [1 ]
Tuna, Floriana [2 ,3 ]
McInnes, Eric J. L. [2 ,3 ]
Lewis, William [1 ]
Blake, Alexander J. [1 ]
Liddle, Stephen T. [1 ]
机构：
[1] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England
[2] Univ Manchester, Sch Chem, EPSRC Natl UK EPR Facil, Manchester M13 9PL, Lancs, England
[3] Univ Manchester, Photon Sci Inst, Manchester M13 9PL, Lancs, England
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 15期
基金：
英国工程与自然科学研究理事会;
关键词：
VALENT ORGANOURANIUM COMPLEXES; NITROGEN MULTIPLE BOND; URANYL-ION; MOLECULAR-STRUCTURE; ELEMENT COMPLEXES; FUNCTIONAL-GROUPS; INFRARED-SPECTRA; RHENIUM COMPLEX; REACTIVITY; CRYSTAL;
D O I：
10.1021/ja502405e
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Deprotonation of [U(Tren(TIPS))(NH2)] (1) [Tren(TIPS) = N(CH2CH2NSiPr3i)(3)] with organoalkali metal reagents MR (M = Li, R = Bu-t; M = Na-Cs, R = CH2C6H5) afforded the imido-bridged dimers [{U(Tren(TIPS)(mu-N[H]M)}(2)] [M = Li-Cs (2a-e)]. Treatment of 2c (M = K) with 2 equiv of 15-crown-S 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 sigma(2)pi(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).
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页码：5619 / 5622
页数：4
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