| 223508-95-0

• CAS: 223508-95-0
• 化学式: C₃₀H₄₄U
• 分子量: 642.708
• InChiKey: MOKFEXOPPMEBKB-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-甲基-1-丁炔 以 苯 为溶剂， 生成
  参考文献：
  名称：

  有机act系元素促进的末端炔烃的催化氢化硅烷化

  摘要：

  已经发现类型为Cp * 2 AnMe 2（An = Th，U）的有机act素络合物是末端炔烃氢化硅烷化的有效催化剂。反应的化学选择性和区域专一性在很大程度上取决于催化剂的性质，炔烃的性质，硅烷取代基，硅烷与炔烃的比例，溶剂以及反应温度。在室温下，末端炔烃与PhSiH 3的氢化硅烷化反应将反式乙烯基硅烷与甲硅烷基炔烃和相应的烯烃一起作为主要产物。在较高温度（50-80°C）下，除室温下获得的产品外，顺式得到-乙烯基硅烷和其中两个硅部分连接在相同碳原子上的双氢化硅烷化的烯烃。发现（TMS）CvinCH和PhSiH 3与Cp * 2 ThMe 2的催化氢化硅烷化仅在较高温度下进行，尽管未观察到顺式乙烯基硅烷或双氢化硅烷化产物。当催化氢化硅烷化反应是使用1：2的比例的我将PrC⋮CH转化为具有Cp * 2 ThMe 2的PhSiH 3，双氢化硅烷化产物的产率从6％提高至26％。之间1的比例：当相同

  DOI：

  10.1021/om990655c

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.