[Th{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)] | 238735-77-8

• 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: [Th{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)]
• 英文别名: 2-[bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;thorium(4+);iodide
• CAS: 238735-77-8
• 化学式: C₂₄H₅₇IN₄Si₃Th
• 分子量: 844.942
• InChiKey: KGNWMCWDDQUHRU-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：

  [Th{N(CH₂CH₂NSiMe₂Bu^t)₃}(I)] 在 potassium 作用下， 以 正戊烷 为溶剂， 以22%的产率得到Th(N(CH₂CH₂NSi(CH₃)2(C(CH₃)3))2(CH₂CH₂NSi(CH₃)(C(CH₃)3)CH₂))
  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
• 作为产物：
  描述：

  碘代三甲硅烷 、 以 正戊烷 为溶剂， 以90%的产率得到[Th{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