[(pentamethylcyclopentadienyl)2U(CCPh)2] | 180310-31-0

• 英文名称: [(pentamethylcyclopentadienyl)2U(CCPh)2]
• 英文别名: [U(CCPh)2(pentamethylcyclopentadienyl)2]
• CAS: 180310-31-0
• 化学式: C₃₆H₄₀U
• 分子量: 710.742
• InChiKey: VQCPIGAZBRUYED-UHFFFAOYSA-N

计算性质

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

• 作为反应物：
  描述：

  [(pentamethylcyclopentadienyl)2U(CCPh)2] 、 N,N'-二异丙基碳二亚胺 以 甲基环己烷 为溶剂， 以96%的产率得到[U(pentamethylcyclopentadienyl)2(CCPh)((i-Pr)NC(CCPh)N(i-Pr)-κ2N,N')
  参考文献：
  名称：

  将碳二亚胺和有机叠氮化物插入到Act系碳键中

  摘要：

  通过研究碳二亚胺（RN═C═NR）和有机叠氮化物（RN 3）与act系烷基，炔基和芳基配合物的插入化学，探索了对有机act系络合物中空间拥挤的操纵。我PrN═C═N我镨发生反应与（C 5我5）2 ANME 2，以产生同晶甲基脒基（C 5我5）2 ANME [（我PR）NC（ME）N（我PR）-κ 2 N，N']，An = Th，1 ; U，2，高产。的反应我PrN═C═N我Pr与（C 5 Me 5）2 U（C≡CPh）2形成相似的插入产物，（C 5 Me 5）2 U（C≡CPh）[（i Pr）NC（C≡CPh）N（i Pr ）-κ 2 N，N']，3。（C 5我5）2 ù（C 6 H ^ 5）2不会产生类似的产物与我PrN═C═N我PR，但形式而不是复杂的形式上从碳二亚胺衍生插入到一个“（C 5我5）2个U（C 6 H 4）”中间体，（C 5 Me 5）2 U [（i Pr）NC═N（i Pr）（C

  DOI：

  10.1021/om900135e
• 作为产物：
  描述：

  、 苯乙炔 以 四氢呋喃 为溶剂， 生成 [(pentamethylcyclopentadienyl)2U(CCPh)2]
  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.
• Insertion Reactivity of CO₂, PhNCO, Me₃CC≡N, and Me₃CN≡C with the Uranium−Alkynyl Bonds in (C₅Me₅)₂U(C≡CPh)₂
  作者：William J. Evans、Justin R. Walensky、Joseph W. Ziller

  DOI：10.1021/om901006t

  日期：2010.2.22

  The insertion reactivity of (C5Me5)(2)U(C CPh)(2), 1, has been studied with CO2, PhNCO, Me-3-CC N, and Me3CN C. Insertion into both U-C CPh bonds of 1 occurs with the first three substrates to form (C5Me5)(2)U(O2CC CPh)(2), 2, (C5Me5)(2)U[PhNC(C CPh)O-kappa N-2,O](2), 3, and (C5Me5)(2)U[N=C(CMe3)(C CPh)](2), 4, respectively. Only 1 equiv of Me3CN C reacts with1I to form (C5Me5)(2)[(PhC C)C=N(CMe3)-eta C-2,N]U(C CPh), 5, a result similar to the (PrN)-Pr-i=C=(NPr)-Pr-i insertion that forms (C5Me5)(2)[(PrNC)-Pr-i(C CPh)(NPr)-Pr-i-kappa N-2,N']U(C CPh), 6.