| 180310-32-1

• CAS: 180310-32-1
• 化学式: C₃₂H₄₈U
• 分子量: 670.762
• InChiKey: CTHJCGZMVRPQSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  dimethylbis(η5-pentamethylcyclopentadienyl)uranium 、 3,3-二甲基-1-丁炔 以 四氢呋喃 为溶剂， 以99%的产率得到
  参考文献：
  名称：

  铀（IV）双（酰胺基），亚氨基和双（乙酰胺）配合物：合成，分子结构，溶液动力学和相互转化反应

  摘要：

  [UMe 2（C 5 Me 5）2 ]与伯芳族或脂族胺的反应导致单体铀（IV）配合物[U（C 5 Me 5）2（NHR）2 ]（R = 2的快速形成）2,6-二甲基苯基1，等2或卜吨3）。通过标准技术对化合物进行表征，对于1，通过X射线衍射进行表征。在配位溶剂中，例如四氢呋喃（thf），化合物1在分子内反应释放一种伯胺并形成亚氨基铀（IV）[U（C5 Me 5） 2 {N（C 6 H 3 Me 2 -2,6）}]·thf 4，而在非配位溶剂中，无碱的[U（C 5 Me 5） 2 {N（C获得6 H 3 Me 2 -2,6）}] 5。发现4中的thf与本体溶剂不平衡，并且观察到居里·魏斯行为后，加成碱的不同质子化学位移随温度的变化而变化。双（酰胺基）和/或亚氨基配合物与末端炔烃的σ-键易位反应产生了双（乙酰胺）配合物[U（C5我5） 2（CCR） 2 ]（R =苯基6或卜吨7）为末端炔烃的区

  DOI：

  10.1039/dt9960002541

文献信息

• Oligomerization and Cross-Oligomerization of Terminal Alkynes Catalyzed by Organoactinide Complexes
  作者：Ariel Haskel、Thomas Straub、Aswini K. Dash、Moris S. Eisen

  DOI：10.1021/ja9836390

  日期：1999.4.1

  Various organoactinides of the type Cp*(2)An(C=CR)(2) (Cp* = C(5)Me(5); An = Th, U) have been synthesized from the corresponding Cp*(2)AnMe(2) complexes by addition of an equimolar amount or an excess of the corresponding terminal alkyne. Attempts to trap the mono(acetylide) complexes Cp*(2)An(C=CR)(Me) were successful for only the transient species Cp*(2)U(C=C(i-Pr))(Me). The bis(acetylide) complexes are active catalysts for the linear oligomerization of terminal alkynes HC=CR. The regioselectivity and the extent of oligomerization depend strongly on the alkyne substituent R, whereas the catalytic reactivities are similar for both organoactinides. Reaction with tert-butylacetylene regioselectively yields the 2,4-disubstituted 1-butene-3-yne dimer, whereas (trimethylsilyl)acetylene is regioselectively trimerized to (E,E)-1,4,6-tris(trimethylsilyl)-1,3-hexadiene-5-yne, with small amounts (3-5%) of the corresponding 2,4-disubstituted 1-butene-3-yne dimer. Oligomerization with less bulky alkyl- and aryl-substituted alkynes produces a mixture of oligomers. Cross-oligomerizations reactions induce the formation of specific cross dimers and trimers. Mechanistic studies on the selective trimerization of HC=CSiMe(3) show that the first step in the catalytic cycle is the C=C bond insertion of the terminal alkyne into the actinide-acetylide bond. The kinetic rate law is first order in organoactinide and in alkyne, with Delta H(double dagger) = 11.1(3) kcal mol(-1) and Delta S(double dagger) = - 45.2(6) eu. The turnover-limiting step is the release of the organic oligomer from the alkenyl-actinide complex. The latter key organometallic intermediate has been characterized by spectroscopic and poisoning studies. A plausible mechanistic scenario is proposed for the oligomerization of terminal alkynes.