(C₅Me₅H)₂UCl₂ | 853913-68-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: (C₅Me₅H)₂UCl₂
• 英文别名: UCl2(tetramethylcyclopentadienyl)2；1,2,3,5-Tetramethylcyclopenta-1,3-diene;uranium(4+);dichloride
• CAS: 853913-68-5
• 化学式: C₁₈H₂₆Cl₂U
• 分子量: 551.339
• InChiKey: NIWVBDUYNFEVMY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -0.71
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (C₅Me₅H)₂UCl₂ 、 四丁基氯化铵 以 苯 为溶剂， 反应 2.0h， 以302 mg的产率得到[NBu₄][(C₅Me₄H)₂UCl₃]
  参考文献：
  名称：

  四丁基铵盐在铀茂金属化学中的合成效用

  摘要：

  Tetrabutylammonium chloride and nitrate salts react with (C5Me5)(2)UCl2 to expand the coordination sphere of the metallocene to form the formal 9- and 10-coordinate complexes, [NBu4][(C5Me5)(2)UCl2(NO3)], 1, and [NBu4][(C5Me5)(2)UCl2(NO3)], 2, respectively. Complex 2 displays modified reactivity compared to that of (C5Me5)(2)UCl2 in substitution reactions with Khpp [hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido(1,2-a)pyrimidine] and K(NC4Me4) in the synthesis of (C5Me5)(2)U(hpp)Cl, (C5Me5)U(hpp)(3), and (C5Me5)(2)U(NC4Me4)Cl. The U3+ complex, [NBu4][(C5Me5)(2)UCl2], can be formed by reduction of 2 with K(Hg), as well as with KC5Me5, K2C8H8, and Li3N.

  DOI：

  10.1021/acs.organomet.5b00942
• 作为产物：
  描述：

  [NBu₄][(C₅Me₅)₂UCl₃] 在 四苯硼钠 作用下， 生成 (C₅Me₅H)₂UCl₂
  参考文献：
  名称：

  四丁基铵盐在铀茂金属化学中的合成效用

  摘要：

  Tetrabutylammonium chloride and nitrate salts react with (C5Me5)(2)UCl2 to expand the coordination sphere of the metallocene to form the formal 9- and 10-coordinate complexes, [NBu4][(C5Me5)(2)UCl2(NO3)], 1, and [NBu4][(C5Me5)(2)UCl2(NO3)], 2, respectively. Complex 2 displays modified reactivity compared to that of (C5Me5)(2)UCl2 in substitution reactions with Khpp [hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido(1,2-a)pyrimidine] and K(NC4Me4) in the synthesis of (C5Me5)(2)U(hpp)Cl, (C5Me5)U(hpp)(3), and (C5Me5)(2)U(NC4Me4)Cl. The U3+ complex, [NBu4][(C5Me5)(2)UCl2], can be formed by reduction of 2 with K(Hg), as well as with KC5Me5, K2C8H8, and Li3N.

  DOI：

  10.1021/acs.organomet.5b00942

文献信息

• Synthesis and Structure of the Bis(tetramethylcyclopentadienyl)uranium Metallocenes (C₅Me₄H)₂UMe₂, (C₅Me₄H)₂UMeCl, [(C₅Me₄H)₂U][(μ-η⁶:η¹-Ph)(μ-η¹:η¹-Ph)BPh₂], and [(C₅Me₄)SiMe₂(CH₂CHCH₂)]₂UI(THF)
  作者：William J. Evans、Stosh A. Kozimor、Wes R. Hillman、Joseph W. Ziller

  DOI：10.1021/om050462r

  日期：2005.9.1

  methyl complexes (C5Me4H)2UMe2 (2) and (C5Me4H)2UMeCl (3), both of which were characterized by X-ray crystallography. Complex 3 can also be synthesized by ligand redistribution between 1 and 2. Complex 2 is easily reduced with potassium to form (C5Me4H)2UMe2K (4), which provides entry into unsolvated bis(tetramethylcyclopentadienyl) U(III) chemistry. Complex 4 reacts with 2 equiv of Et3NHBPh4 to form the

  尽管已经广泛地研究了双（五甲基环戊二烯基）铀茂金属化学，但是对双（四甲基环戊二烯基）类似物的反应性知之甚少。为了提供必需的（C 5 Me 4 H）2 U配合物与（C 5 Me 5）2 U配合物进行比较，已制备了一系列双（四甲基环戊二烯基）铀配合物。最近分离出的（C 5 Me 4 H）2 UCl 2（1）与MeLi反应形成甲基络合物（C 5 Me 4 H）2UMe 2（2）和（C 5 Me 4 H）2 UMeCl（3）均通过X射线晶体学表征。配合物3也可以通过1和2之间的配体重新分布来合成。配合物2容易被钾还原形成（C 5 Me 4 H）2 UMe 2 K（4），从而可以进入未溶剂化的双（四甲基环戊二烯基）U（III）化学。配合物4与2当量的Et 3 NHBPh 4反应形成三价阳离子配合物[（C 5 Me 4 H）2 U] [（μ-Ph）2 BPh 2 ]（5），其结构与[（C 5 Me 5
• Two-electron reductive reactivity of trivalent uranium tetraphenylborate complexes of (C5Me5)1− and (C5Me4H)1−
  作者：William J. Evans、Kevin A. Miller、Wes R. Hillman、Joseph W. Ziller

  DOI：10.1016/j.jorganchem.2007.04.046

  日期：2007.8

  The reductive reactivity of the (BPh4)1− ligand in pentamethylcyclopentadienyl [(C5Me5)2U][(μ-η2:η1-Ph)2BPh2] (1) was compared with that of the tetramethyl analog, [(C5Me4H)2U][(μ-η6:η1-Ph)(μ-η1:η1-Ph)BPh2] (2) using PhSSPh as a probe to determine if the mode of (BPh4)1− bonding affected the reduction. Both complexes act as two-electron reductants to form (C5Me4R)2U(SPh)2 [R = Me, 3; H, 4], but only

  的（BPH的还原反应4）1-配体在五甲基环戊二烯[（C 5我5）2 C] [（μ-η 2：η 1 -Ph）2 BPH 2 ]（1）中的溶液与四甲基相比类似物，[（C 5我4 1H）2 C] [（μ-η 6：η 1 -Ph）（μ-η 1：η 1 -Ph）BPH 2 ]（2）使用PhSSPh作为探针，以确定是否（BPh 4）1−的模式粘合影响了还原。两种络合物均充当双电子还原剂，形成（C 5 Me 4 R）2 U（SPh）2 [R = Me，3 ; H，4 ]，但是只有在R ＝ H的情况下，才能对产物进行结晶学表征。还报道了由[（C 5 Me 5）2 UH] 2（5）和[Et 3 NH] [BPh 4 ]合成1的改进方法，以及它与MeCN的反应，这提供了另一条通往异常，平行反应的途径。环，金属茂铀[（C 5 Me 5）2U（NCMe）5 ] [BPh 4 ] 2（6）。
• Facile Syntheses of Unsolvated UI₃ and Tetramethylcyclopentadienyl Uranium Halides
  作者：William J. Evans、Stosh A. Kozimor、Joseph W. Ziller、Anatolii A. Fagin、Mikhail N. Bochkarev

  DOI：10.1021/ic0482685

  日期：2005.5.1

  In the course of comparing the reaction chemistry of (C5Me5)(3)U, 1, and its slightly less crowded analogue (C5Me4H)(3)U, 2, new syntheses of Ul(3), (C5Me4H)(3)U, (C5Me4H)(3)UCl, 3, and (C5Me5)(3)UCl, 4, have been developed. Additionally, (C5Me4H)(3)Ul, 5, and (C5Me4H)(2)UCl2, 6, have been identified for the first time. A facile synthesis of unsolvated Ul(3) is reported that proceeds in high yield with inexpensive equipment from iodine and hot uranium turnings. Both Ul(3) and Ul(3)(THF)(4) react with KC5Me4H in toluene to make unsolvated (C5Me4H)(3)U in higher yield than in previous reports that involve reduction of tetravalent (C5Me4H)(3)UCl, 3. A more atom-efficient synthesis of complex 3 is also reported that proceeds from reduction of t-BuCl, PhCl, or HgCl2 by 2. Similarly, (C5Me4H)(3)U reacts with Phl or Hgl(2) to generate (C5Me4H)(3)Ul. These studies also provided a basis to improve the synthesis of (C5Me5)(3)UCl from 1 by employing t-BuCl or HgCl2 as the halide source. Like (C5Me5)(3)UCl, the (C5Me4H)(3)UCl Complex reacts with HgCl2 to form (C5Me4H)(2) and (C5Me4H)(2)UCl2, 6, but unlike (C5Me5)(3)UX (X = Cl or l), the less substituted (C5Me4H)(3)UX complexes do not reduce t-BuCl or PhX. The synthesis of 6 from (C5Me4H)MgCl-THF and UCl4 is also included.