(trimethylsilylcyclopentadienyl)zirconium trichloride | 756863-61-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (trimethylsilylcyclopentadienyl)zirconium trichloride
• 英文别名: Cyclopenta-2,4-dien-1-yl(trimethyl)silane;zirconium(4+);trichloride
• CAS: 756863-61-3
• 化学式: C₈H₁₃Cl₃SiZr
• 分子量: 334.86
• InChiKey: UVGIXECMTKHGQQ-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -7.04
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  (trimethylsilylcyclopentadienyl)zirconium trichloride 、 2-(4-methoxyphenyl)-4,5,6,7-tetrahydroindene 在 正丁基锂 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 8.0h， 以51%的产率得到[2-(4-methoxyphenyl)-4,5,6,7-tetrahydroindenyl](trimethylsilylcyclopentadienyl)zirconium dichloride
  参考文献：
  名称：

  具有 4,5,6,7-四氢茚配体的新型二茂锆。乙烯聚合及乙烯与己-1-烯共聚的合成及催化活性

  摘要：

  通过ZrCl4或(CpTMS)ZrCl3与相应四氢茚的锂盐反应，得到了一系列对称和非对称的四氢茚基锆配合物。用甲基铝氧烷活化，这些配合物在乙烯聚合（高达 6.8∙106 g PE (mol Zr h)–1）以及乙烯和己-1-烯的共聚（高达 8.6∙106 g PE (mol Zr h)–1)。

  DOI：

  10.1007/s11172-016-1485-x
• 作为产物：
  描述：

  三甲硅烷基环戊二烯 、 氯化锆(IV) 在 正丁基锂 、 三甲基氯硅烷 作用下， 以 乙醚 、 正己烷 、 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 以18.3 g的产率得到(trimethylsilylcyclopentadienyl)zirconium trichloride
  参考文献：
  名称：

  具有 4,5,6,7-四氢茚配体的新型二茂锆。乙烯聚合及乙烯与己-1-烯共聚的合成及催化活性

  摘要：

  通过ZrCl4或(CpTMS)ZrCl3与相应四氢茚的锂盐反应，得到了一系列对称和非对称的四氢茚基锆配合物。用甲基铝氧烷活化，这些配合物在乙烯聚合（高达 6.8∙106 g PE (mol Zr h)–1）以及乙烯和己-1-烯的共聚（高达 8.6∙106 g PE (mol Zr h)–1)。

  DOI：

  10.1007/s11172-016-1485-x

文献信息

• Mono- and di-cyclopentadienyl zirconium derivatives containing the dimethylsilylcyclopentadienyl ligand. Agostic linear Si–H–Zr interaction in the molecular structure of [Zr{η5-C5H4(SiMe2H)}Cl3]2 †
  作者：Gemma Ciruelo、Tomás Cuenca、Rafael Gómez、Pilar Gómez-Sal‡、Avelino Martín ‡

  DOI：10.1039/b010221k

  日期：——

  Dimethylsilyl substituted mono- and di-cyclopentadienyl zirconium chlorides have been prepared and their reactions with amido and alkyl reagents studied. The silylcyclopentadienes C5H5(SiMe2H) 1, C5H4(SiMe2H)22 and C5H4(SiMe3)(SiMe2H) 3 can be prepared by reaction of Na(C5H5) with the appropriate chlorosilane reagent. The lithium salt Li[C5H4(SiMe2H)] reacts with ZrCl4 or [Zr(C5H5)Cl3] to give the metallocene complexes [Zr(C5H4R)C5H4(SiMe2H)}Cl2] (R = SiMe2H 4 or H 5) whereas the reaction of the disilylcyclopentadiene C5H4(SiMe2H)2 with ZrCl4 afforded the monocyclopentadienyl complex [ZrC5H4(SiMe2H)}Cl3] 6, which exchanges the Si–H and Zr–Cl bonds. The reaction of 6 with lithium amides produces different products depending on the basicity of the nitrogen atom and the steric demands of its amido substituents. The reaction with LiN(SiMe3)2 and LiNH(2,6-Me2C6H3) afforded the corresponding amido zirconium complexes [ZrC5H4(SiMe2H)}(NRR′)Cl2] (R = R′ = SiMe37; R = H, R′ = 2,6-Me2C6H38), but in the case of the reaction with LiNHtBu the known cyclopentadienylsilylamido derivative [Zr(η5,η1-C5H4SiMe2NtBu)Cl2] was formed. The monoamido, diamido and dialkyl dicyclopentadienyl complexes [Zr(C5H4R)C5H4(SiMe2H)}X(Y)] (R = SiMe2H 9 or H 10, X = Cl, Y = NHtBu; R = SiMe2H 11 or H 12, X = Y = NHtBu; R = SiMe2H 13 or H 14, X = Y = Me) have been synthesized by reaction of 4 and 5 with the appropriate amido or methyl reagent. Compound 9 reacts with a stoichiometric amount of water with selective hydrolysis of the Zr–amido bond to give the corresponding μ-oxo dinuclear complex [Zr[C5H4(SiMe2H)]2Cl}2(μ-O)] 15. The molecular structure of [ZrC5H4(SiMe2H)}Cl3] 6 was established by X-ray crystallography. Compound 6 is a dimer, in the solid state, in which dimerization occurs through Zr–H–Si agostic interactions and two chloride bridges.

  已经制备了二甲基硅烷取代的单环戊二烯基和二环戊二烯基锆氯化物，并研究了它们与氨基和烷基试剂的反应。通过Na(C5H5)与适当的氯硅烷试剂反应，可以制备硅基环戊二烯 (SiMe2H) 1、C5H4(SiMe2H)22和 (SiMe3)(SiMe2H) 3。锂盐Li[ (SiMe2H)]与ZrCl4或[Zr( )Cl3]反应，得到金属茂配合物[Zr( R) (SiMe2H)}Cl2]（R = SiMe2H 4或H 5），而二硅基环戊二烯 (SiMe2H)2与ZrCl4反应得到单环戊二烯基配合物[Zr (SiMe2H)}Cl3] 6，该配合物交换了Si–H和Zr–Cl键。6与锂胺反应，根据氮原子的碱性和其氨基取代基的立体要求，产生不同的产物。与LiN(SiMe3)2和LiNH(2,6-Me2C6H3)反应得到相应的氨基锆配合物[Zr (SiMe2H)}(NRR')Cl2]（R = R' = SiMe37；R = H，R' = 2,6-Me2C6H38），但在与LiNHtBu反应的情况下，形成了已知的环戊二烯基硅基氨基衍生物[Zr(η5,η1- SiMe2NtBu)Cl2]。通过4和5与适当的氨基或甲基试剂反应，合成了单氨基、二氨基和二烷基二环戊二烯基配合物[Zr( R) (SiMe2H)}X(Y)]（R = SiMe2H 9或H 10，X = Cl，Y = NHtBu；R = SiMe2H 11或H 12，X = Y = NHtBu；R = SiMe2H 13或H 14，X = Y = Me）。化合物9与化学计量水反应，选择性水解Zr–氨基键，得到相应的μ-氧二核配合物[Zr[ (SiMe2H)]2Cl}2(μ-O)] 15。通过X射线晶体学确定了[Zr (SiMe2H)}Cl3] 6的分子结构。化合物6在固态下是二聚体，二聚化通过Zr–H–Si暂稳相互作用和两个氯桥实现。
• Role of Amine Structure and Site Isolation on the Performance of Aminosilica-Immobilized Zirconium CGC-Inspired Ethylene Polymerization Catalysts
  作者：Kunquan Yu、Michael W. McKittrick、Christopher W. Jones

  DOI：10.1021/om049765w

  日期：2004.8.1

  The homogeneous zirconium complex (CpSiMe2Cl)ZrCl3 is immobilized onto three different aminosilica supports, resulting in supported constrained-geometry-inspired zirconium complexes that, when combined with methylalumoxane (MAO), are active for the homopolymerization of ethylene to produce linear polyethylenes. The structure of the immobilized metal species is shown to depend on both the nature of the amine groups on the surface (primary vs secondary) and the amine surface density (densely loaded vs site-isolated). Diffuse-reflectance ultraviolet-visible (UV-vis) spectra of the metallated solids indicates that a true, immobilized constrained-geometry catalyst (CGC) is likely only produced on the silica that contains isolated primary amine sites. The polymerization data support the hypothesis that a traditional constrained-geometry Zr catalyst exhibits higher catalytic activity compared to a more open metal center that is likely the primary species produced on a densely loaded aminosilica surface. MAO causes significant leaching of the immobilized catalysts, possibly due to the cleavage of the Si-O-Si surface linkage.