2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;diethylazanide;uranium(4+) | 238735-78-9

• 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: 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;diethylazanide;uranium(4+)
• CAS: 238735-78-9
• 化学式: C₂₈H₆₇N₅Si₃U
• 分子量: 796.159
• InChiKey: PFKNDUPFGYXPRT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.83
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  7.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  三氯化硼 、 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;diethylazanide;uranium(4+) 以 氘代苯 为溶剂， 生成 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);chloride
  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
• 作为产物：
  描述：

  以 not given 为溶剂， 生成 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;diethylazanide;uranium(4+)
  参考文献：
  名称：

  Synthesis of a highly strained uranacycle: molecular structures of organometallic products arising from reduction, oxidation and protonolysis

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(99)00453-2

文献信息

• 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。