[U{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)] | 220408-25-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [U{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)]
• 英文别名: 2-[bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);iodide
• CAS: 220408-25-3
• 化学式: C₂₄H₅₇IN₄Si₃U
• 分子量: 850.933
• InChiKey: VPYUREIRYHZQSR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.43
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [U{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)] 在 potassium 作用下， 以 氘代苯 、 正戊烷 为溶剂， 生成
  参考文献：
  名称：

  Reactivity of a triamidoamine complex of trivalent uranium

  摘要：

  在戊烷中用钾还原 [U(NN′3)I] [NN′3 = N(CH2CH2NSiMe2But)3] 得到紫色三价单体 [U(NN′3)]，收率很高，这种化合物之前是通过混合价 [{U(NN′3)}2(μ-Cl)] 的分馏真空升华合成的。这种化合物的磁感应强度与 U（III）中心的存在相吻合，其特征性的近红外光谱也证实了这一点。报告还介绍了它与路易斯碱反应生成[U(NN′3)(Py)]和[U(NN′3)(HMPA)]的情况，以及后者的分子结构。复合物[U(NN′3)]很容易氧化，分别与三甲基硅叠氮化物和二氮甲烷反应很容易形成亚氨基和酰肼络合物。然而，与亚甲基三甲基磷丙烷反应会生成加成化合物[U(NN′3)(CH2PMe3)]。后一种复合物与空气反应后，产生了一些不常见的羟基复合物[U(NN′3)(OH)(CH2PMe3)]晶体，并确定了其结构特征。U(NN′3)(CH2PMe3)]与三甲胺 N-氧化物反应产生了五价[U(NN′3)(O)]，或许是其二聚体。后者与[U(NN′3)]反应生成桥接氧配合物[{U(NN′3)}2(μ-O)]，该配合物也可以通过三甲胺 N-氧化物与[U(NN′3)]反应直接制备。

  DOI：

  10.1039/b108584k
• 作为产物：
  描述：

  碘代三甲硅烷 、 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);chloride 以 正戊烷 为溶剂， 以96%的产率得到[U{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)]
  参考文献：
  名称：

  Triamidoamines与早期Act系元素的配合物。含卤化物和酰胺配体的四价铀和Thor单体化合物的合成路线。

  摘要：

  锂化三酰氨基胺[Li（3）（NN'（3））（THF）（3）] [NN'（3）= N（CH（2）CH（2）NSiMe（2）Bu（t） ）（3）]与AnCl（4）（An = U，Th），然后升华，得到单体[An（NN'（3））Cl]。这些配合物与SiMe（3）X（X = Br，I）反应得到[An（NN'（3））X]。酰胺衍生物[An（NN'（3））（NEt（2））]由H（3）（NN'（3））和[U（NEt（2））（4）]和[Th （NN'（3））Cl]和[Li（NEt（2））]。在每种情况下，复合物[U（NN'（3））X]（X = Cl，Br，I，NEt（2））均通过X射线晶体学显示含有三酰胺对称的三酰胺基配体。金属中心。由于铀原子从三个酰胺基氮原子的赤道平面移出了大约20个，从而使结构从三角形双锥体中变形了。0.8Å。配体主链以一种方式变形，以致使叔丁基二甲基甲硅烷基包围金属原子的赤道平面，

  DOI：

  10.1021/ic990563f

文献信息

• Thorium- and uranium-azide reductions: a transient dithorium-nitride <i>versus</i> isolable diuranium-nitrides
  作者：Jingzhen Du、David M. King、Lucile Chatelain、Erli Lu、Floriana Tuna、Eric J. L. McInnes、Ashley J. Wooles、Laurent Maron、Stephen T. Liddle

  DOI：10.1039/c8sc05473h

  日期：——

  (M = U, 1; Th, 2; TrenDMBS = N(CH2CH2NSiMe2But)3}3−) with NaN3 or KN3, respectively, affords very rare examples of actinide molecular square and triangle complexes [M(TrenDMBS)(μ-N3)}n] (M = U, n = 4, 3; Th, n = 3, 4). Chemical reduction of 3 produces [U(TrenDMBS)}2(μ-N)][K(THF)6] (5) and [U(TrenDMBS)}2(μ-N)] (6), whereas photolysis produces exclusively 6. Complexes 5 and 6 can be reversibly inter-converted

  分子铀氮化物现在是众所周知的，但在低温基质分离实验之外没有可分离的分子氮化钍。我们报告了用NaN 3或_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ KN 3分别提供了非常罕见的锕系分子方形和三角形配合物 [M(Tren DMBS )(μ-N 3 )} n ] (M = U, n = 4, 3; 钍, n = 3, 4 )。3的化学还原产生[U(Tren DMBS )} 2 (μ-N)][K(THF) 6 ] ( 5 )和[U(Tren DMBS )} 2 (μ-N)] ( 6 )，而光解仅产生6。配合物5和6可以分别通过氧化和还原可逆地相互转化，这表明这些 UNU 核心是稳健的，没有观察到任何 C-H 键活化的证据。相反，芳烃或醚类溶剂中4的还原得到 [Th(Tren DMBS )} 2(μ-NH)] ( 7 ) 或 [Th(Tren DMBS )}Th(N[CH
• Structure and reactions of a metallacyclic complex containing a remarkably long uranium–carbon bond
  作者：Rita Boaretto、Paul Roussel、Andrew J. Kingsley、Ian J. Munslow、Christopher J. Sanders、Nathaniel W. Alcock、Peter Scott

  DOI：10.1039/a903783g

  日期：——

  The intramolecular metalation of a β-silyl methyl group in [UN(CH2CH2NSiMe2But)3}(CH2Ph)] occurs rapidly, despite the conformational demands of the triamidoamine ligand, to produce a highly strained metallacycle (U–C ca. 2.75 Å); this complex reacts cleanly with a range of carbon and other acids to give, for example, an alkynyl with a bent (156°) U–CC unit.

  尽管三酰胺胺配体对构象有要求，但[UN(CH2CH2NSiMe2But)3}(CH2Ph)]中β-硅甲基的分子内金属化反应仍迅速发生，生成高度紧张的金属环（U-C约2.75 Å）；该复合物与一系列碳酸和其他酸发生清洁反应，例如，生成具有弯曲（156°）U-CC单元的炔基。
• Synthesis of a highly strained uranacycle: molecular structures of organometallic products arising from reduction, oxidation and protonolysis
  作者：Rita Boaretto、Paul Roussel、Nathaniel W Alcock、Andrew J Kingsley、Ian J Munslow、Christopher J Sanders、Peter Scott

  DOI：10.1016/s0022-328x(99)00453-2

  日期：1999.12

  The reaction of [U(NN3')I] [NN3' = N(CH2CH2NSiMe2Bu')(3)] with Group 1 and 2 metal alkyls gives, via metalation of a methylsilyl group, a highly strained metallacycle [U(bit-NN3')] in high yield. The molecular structure of this compound shows that it has an unusually long U-C bond (ca. 2.75 Angstrom) and additional C-H ... M agostic interactions. On exposure of the complex in solution to H-2(2) the methylsilyl groups and the metallacyclic UCH2Si group are deuterated, leaving the tert-butyl and methylene groups intact. The analogous thorium metallacycle is prepared from the reactions of [Th(NN3')Cl], or by attempted reduction of [Th(NN3')I] with potassium metal in pentane. Attempted reduction of [U(NN3')I] in a similar manner in toluene gave a high yield of a fascinating dimeric metallacyclic anion [K(eta(6)-C6H5Me)][U(bit -NN3')]}(2), which was characterised by X-ray crystallography. The authenticity of this compound as U(III) is established by near-IR spectroscopy, and also by its production from the reaction of the neutral uranacycle [U(bit-NN3')] with potassium. A mechanism for the formation of the anion is postulated. Its reaction with benzyl chloride led to oxidation to the parent uranacycle. Oxidation of [U(bit-NN3')] with air or oxide sources leads to formation of an ore-bridged dimer with intermonomer metalated methylsilyl groups and pentavalent uranium centres. Reactions of [U(bit-NN3')] with a range of acids HX occur rapidly, reprotonating the previously metalated methylsilyl group and forming complexes [U(NN3')X]. For example, lutidinium hydrochloride, diethylamine and tert-butanol gave [(NN3')UCl], [(NN3')U(NEt2)] and [(NN3')U(OBut)], respectively. Reactions with carbon acids were also successful. For example, beta-hydropyridines gave eta(2)-dehydropyridyl complexes. One of these, [U(NN3')(eta(2)-NC5H4)], is shown in the first X-ray crystallographic study of such an actinide complex to contain an essentially planar U(eta(2)-NC5H4) unit. Monosubstituted alkynes react with the uranacycle in a similar manner to give eta(1)-alkynyls. The molecular structure of one example shows that the U-C=C unit is bent (156 degrees) in contrast to other structurally characterised non-bridging alkynyls of the f-elements. (C) 1999 Elsevier Science S.A. All rights reserved.