Cp2Zr(μ-Cl)(μ-C2B10H10)Li(OEt2)2 | 868632-37-5

• 英文名称: Cp2Zr(μ-Cl)(μ-C2B10H10)Li(OEt2)2
• 英文别名: Cp₂Zr(μ-Cl)(μ-C₂B₁₀H₁₀)Li(OEt₂)₂；Cp2Zr(μ-Cl)(μ-C2B₁₀H₁₀)Li(OEt₂)₂；(η5-cyclopentadienyl)2Zr(μ-Cl)(μ-C2B10H10)Li(OEt2)2；Cp2Zr(μ-Cl)(μ-1,2-C2B10H10)Li(OEt2)2
• CAS: 868632-37-5
• 化学式: C₂₀H₄₀B₁₀ClLiO₂Zr
• 分子量: 554.264
• InChiKey: BFTFAVBYIVXUDJ-UHFFFAOYSA-M

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

• 作为反应物：
  描述：

  Cp2Zr(μ-Cl)(μ-C2B10H10)Li(OEt2)2 、 2-甲基-1-己烯-3-炔 以 甲苯 为溶剂， 以46%的产率得到1,2-[(η5-cyclopentadienyl)2ZrC[C(Me)=CH2]=C(Et)]-1,2-C2B10H10
  参考文献：
  名称：

  锆茂-碳炔前体与炔烃的反应：结合碳硼烷基单元的氧化锆环戊烯的有效途径。

  摘要：

  的反应锆-carboryne前体的Cp 2 Zr的（μ-Cl）的（μ-C 2乙10 ħ 10）立（OET 2）2与各种炔[R 1 C≡CR 2在回流的甲苯中给出monoinsertion产品1， 2- [Cp 2 ZrC（R 1）═C（R 2）]-1,2-C 2 B 10 H 10具有良好的化学选择性和区域选择性，分离出的收率很高或很高。该反应提供了结合有碳硼烷基单元的氧化锆环戊烯的有效途径，该碳硼烷基单元是氧化锆环戊二烯的碳硼烷形式。所有配合物已通过各种光谱技术和单晶X射线分析得到充分表征。

  DOI：

  10.1021/om9002973
• 作为产物：
  描述：

  正丁基锂 、 二氯二茂锆 、 1,2-dicarba-closo-dodecaborane(12) 以 乙醚 为溶剂， 以70%的产率得到Cp2Zr(μ-Cl)(μ-C2B10H10)Li(OEt2)2
  参考文献：
  名称：

  锆茂-碳炔前驱体的合成、结构和反应性

  摘要：

  过渡金属-苄配合物在有机合成、机理研究和功能材料的合成中有许多应用。与此形成鲜明对比的是，过渡金属-碳炔配合物的反应化学实际上是未知的，尽管理论计算表明碳炔 (1,2-C2B10H10) 和苄的形成在能量上非常相似。本通讯报道了一种新型锆茂-碳硼烷复合物 Cp2Zr(mu-Cl)(mu-C2B10H10)Li(OEt2)2 (1)，它是锆茂-碳硼炔物种的有效前体，由 Cp2ZrCl2 与 1 当量的 Li2C2B10H10 反应制备在 Et2O 中。反应性研究表明，1 在与极性不饱和有机分子的反应中类似于二茂锆 - 苄。另一方面，它对炔烃和烯烃没有反应性，一种与二茂锆-苯完全不同的反应模式。这项工作还提供了一种制备功能性邻碳硼烷及其金属配合物的新方法，这些方法无法通过目前已知的其他方法合成。

  DOI：

  10.1021/ja054207+

文献信息

• Synthesis of carborane-fused cyclobutenes and cyclobutanes
  作者：YingGen Yuan、ShiKuo Ren、ZaoZao Qiu、ShaoWu Wang、ZuoWei Xie

  DOI：10.1007/s11426-014-5112-0

  日期：2014.8

  zirconacycles to Cu(II) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu(II) and reductive elimination is proposed.

  碳硼烷稠合的氧化锆环的重金属化成Cu（II）诱导CC偶联反应形成四元环。这是生成一系列碳硼烷稠合的环丁烯和环丁烷的一种新的高效通用方法。提出了一种涉及重金属转化为Cu（II）和还原消除的反应机理。
• Reaction of Zirconocene–Carboryne with Alkenes: Synthesis and Structure of Zirconacyclopentanes with a Carborane Auxiliary
  作者：Shikuo Ren、Zaozao Qiu、Zuowei Xie

  DOI：10.1021/om300202p

  日期：2012.6.25

  auxiliary, which can be viewed as a carborane version of zirconacyclopentanes. They are thermally very stable and chemically inert toward unsaturated organic molecules such as alkenes, alkynes, nitriles, CO, and CO2. All complexes have been fully characterized by various spectroscopic techniques. Some have been further confirmed by single-crystal X-ray analyses.

  锆-carboryne的反应在自CP原位产生2的Zr（μ-Cl）的（μ-C 2乙10 ħ 10）立（OET 2）2与各种烯烃RCH═CH 2在回流的甲苯中，得到的产品monoinsertion 1,2- -[CP 2 ZrCH（R）CH 2 ] -1,2-C 2 B 10 H 10（R =芳基）或1,2- [CP 2 ZrCH 2 CH（R）]-1,2-C 2 B 10小时10（R ＝烷基），取决于烯烃的极性，具有良好的分离产率和很高的区域选择性。该反应提供了一种具有碳硼烷助剂的氧化锆环戊烷的有效途径，可以将其视为氧化锆环戊烷的碳硼烷形式。它们对不饱和有机分子（如烯烃，炔烃，腈，CO和CO 2）具有非常高的热稳定性和化学惰性。所有配合物均已通过各种光谱技术进行了充分表征。一些已经通过单晶X射线分析得到了证实。
• Transition-Metal-Mediated Three-Component Cascade Cyclization: Selective Cage B–C(sp²) Coupling of Carborane with Aromatics and Synthesis of Carborane-Fused Tricyclics
  作者：Yangjian Quan、Zaozao Qiu、Zuowei Xie

  DOI：10.1021/ja503489b

  日期：2014.5.28

  Zirconium/nickel comediated one-pot three-component cascade cyclization of carboryne, alkene, and 2-bromophenyltrimethylsilylacetylene has been achieved, leading to the formation of a series of C,C,B-substituted carborane-fused tricyclics. On the basis of experimental results, a plausible mechanism is proposed including [2 + 2 + 1] cross-cyclotrimerization followed by intramolecular direct selective cage B-C(sp(2)) coupling. This represents the first example of direct cage B-C(phenyl) coupling via cage B-H activation.
• Reaction of a Zirconocene–Carboryne Complex with Pyridines: Ligand C–H Activation
  作者：Shikuo Ren、Zuowei Xie

  DOI：10.1021/om200772q

  日期：2011.11.14

  Reactions of Cp2Zr(mu-Cl)(mu-C2B10H10)Li(OEt2)(2) (1) with various N-heterocycles derived from pyridine were studied. Treatment of 1 with pyridine, 2-bromopyridine, 2, 4-lutidine, quinoline, and 2-(1-hexynyl)pyridine generated alpha-C-H activation (sigma-bond metathesis) products Cp2Zr(eta(2)-C, N-C5H4N) (sigma-C2B10H11) (2), Cp2Zr[eta(2)-C,N-(6-Br-C5H3N)] (sigma-C2B10H11) (3), Cp2Zr[eta(2)-C,N-(4,6-Me-2-C5H2N)](sigma-C2B10H11) (4), Cp2Zr(eta(2)-C,N-C9H6N)(sigma-C2B10H11) (5), and Cp2Zr-eta(2)-C,N-[6-((BuC)-Bu-n C)center dot C5H3N]} (sigma-C2B10H11) (7), respectively. On the other hand, reaction of 1 with acridine gave the addition product 1,2-[Cp2Zr(10,9-C13H9N)]-1,2-C2B10H10 (6) in 85% isolated yield. Complex 1 reacted with 3-(1-hexynyl)pyridine to afford alpha-C-H activation species Cp2Zreta(2)-C,N-[5-((BuC)-Bu-n C)C5H3N]}(sigma-C2B10H11) (8a) and Cp2Zreta(2)-C,N-[3-((BuC)-Bu-n C)C5H3N]}-(sigma-C2B10H11) (8b) in a molar ratio of 42:58, as determined by the H-1 NMR. spectrum. In the presence of CuI, however, the C C insertion products zirconacydopentenes 1,2-[Cp2ZrC(2-C5H4N)=CR]-1,2-C2B10H10 [R = Bu-n (9), Ph (10)] were obtained in 74-77% yields. It is suggested that the coordination of pyridine to the Zr atom is crucial for alpha-C-H activation (sigma-bond metathesis). The presence of CuI can alter the reaction path by preventing the coordination of pyridine to the Zr atom, which blocks the alpha-C-H activation path, leading to the alkyne insertion reaction. All complexes were characterized by H-1, C-13, and B-11 NMR spectra as well as elemental analyses. Their structures were further confirmed by single-crystal X-ray analyses.
• Ren, Shikuo; Chan, Hoi-Shan; Xie, Zuowei, Journal of the American Chemical Society, 2009, vol. 131, p. 3862 - 3863
  作者：Ren, Shikuo、Chan, Hoi-Shan、Xie, Zuowei

  DOI：——

  日期：——