Zr(η(5)-C5H4SiMe2Cl)Cl3 | 159771-54-7

• 英文名称: Zr(η(5)-C5H4SiMe2Cl)Cl3
• 英文别名: ZrCl3(η(5)-C5H4SiMe2Cl)；Zr(η5-C5H4SiClMe2)Cl3
• CAS: 159771-54-7
• 化学式: C₇H₁₀Cl₄SiZr
• 分子量: 355.278
• InChiKey: LMKHSXIWENULSN-UHFFFAOYSA-K

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：

  Zr(η(5)-C5H4SiMe2Cl)Cl3 、 lithium dimethylamide 以 乙醚 为溶剂， 以71%的产率得到Zr(η(5)-C5H4SiMe2NMe2)(NMe2)3
  参考文献：
  名称：

  新型甲硅烷基取代的单环戊二烯基锆配合物的合成和反应性。的透视分子结构中，[Zr η 5 -C 5 H ^ 4（森达2 CH 2 PH）（CH 2 PH）3 ]

  摘要：

  锆（IV）的新的甲硅烷基取代的单环戊二烯基配合物从所述前体合成[Zr的η 5 -C 5 H ^ 4（森达2 Cl）的氯3 ]（1）。的反应1与锂盐苯甲脒基锂[C（PH）N（森达3）2 ]通向配合物[Zr的η 5 -C 5 H ^ 4（森达2 Cl）的C（PH）[N（森达3） ] 2 Cl 2 ]（2），其在溶液中缓慢分解，消除了SiMe 3 Cl。复杂的1种发生反应与烷基，酰氨基和烷氧转移试剂（4当量），得到配合物[Zr的η 5 -C 5 H ^ 4（森达2 X）X 3 ]（X = NME 2（3），OSiMe 3（4）， CH 2 CMe 2 Ph（5），C 6 H 5（6），C 6 F 5（7）和CH 2 SiMe 3（8））收率良好。化合物6和7保留用作溶剂的乙醚，但在高真空条件下将其溶解后即分解。的反应1的Mg（CH 2 PH）2 ·2THF（4当量），得到四苄络合物[Zr的η 5

  DOI：

  10.1016/s0022-328x(97)00443-9
• 作为产物：
  描述：

  1-(chlorodimethylsilyl)-1-(trimethylsilyl)cyclopentadiene 、 氯化锆(IV) 以 甲苯 为溶剂， 以87%的产率得到Zr(η(5)-C5H4SiMe2Cl)Cl3
  参考文献：
  名称：

  Ciruelos, Santiago; Cuenca, Tomás; Gómez-Sal, Pilar, Organometallics, 1995, vol. 14, # 1, p. 177 - 185

  摘要：

  DOI：

文献信息

• Synthesis and Reactivity of [(Amidosilyl)cyclopentadienyl]titanium and -zirconium Complexes. X-ray Molecular Structure of [Zr{η⁵:η¹-C₅H₄SiMe₂(μ-O)}Cl₂{H₂N(CHMe)Ph}]₂
  作者：Santiago Ciruelos、Tomás Cuenca、Rafael Gómez、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1021/om960606p

  日期：1996.12.24

  }Cl2]2 with elimination of alkyl isocyanate OCNR (R = tBu, (±)-CH(Me)Ph) as the unique organic product. Addition of 1 equiv of LiN(SiMe3)2 to a diethyl ether solution of [Zr(η5-C5H4SiMe2Cl)Cl3] (1b) gives the monoamido derivative [Zr(η5-C5H4SiMe2Cl)Cl2N(SiMe3)2}] (2b). The related reaction of the zirconium derivative 1b with LiNHtBu in the presence of NEt3 produces a mixture of two compounds, [Zr

  钛（IV）和锆（IV）的新型半夹心（amidosilyl）环戊二烯基复合物从氯代甲硅烷基取代的环戊二烯基前体的合成[M（η 5 -C 5 H ^ 4森达2 Cl）的氯3 ]（M =的Ti（1a），Zr（1b））。钛[Ti（η的反应5 -C 5 H ^ 4森达2 Cl）的氯3 ]（1A）与LiNHR净的存在3给出了钛[Ti（η 5：η 1 -C 5 ħ 4森达2 NR）氯2]（R = t Bu（2a），（±）-CH（Me）Ph（3a））络合物。类似地，加入2当量的LiN（森达的3）2至复杂1A，得到二酰胺衍生物钛[Ti（η 5 -C 5 H ^ 4森达2 Cl）的氯N（森达3）2 } 2 ] （图4a）。所述amidotitanium复杂钛[Ti（η 5：η 1 -C 5 ħ 4森达2 NH吨丁基）氯2（NH吨丁基）] （5a）中通过使1a与NH 2 t Bu以1：3的摩尔比反应以低收率制
• Synthetic and reactivity studies of mono- and dicyclopentadienyl titanium, zirconium and hafnium complexes with the chlorodimethylsilyl-cyclopentadienyl ligand. X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 and Zr(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl
  作者：Santiago Ciruelos、Alfredo Sebastián、Tomás Cuenca、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1016/s0022-328x(00)00213-8

  日期：2000.6

  Reaction of the disilylated cyclopentadiene C5H4(SiClMe2)(SiMe3) with HfCl4, in heptane, gave the monocyclopentadienyl complex Hf(η5-C5H4SiClMe2)Cl3 (1c). Addition of two equivalents of C5H5(SiClMe2) to a solution of MCl4, in toluene under reflux and in the presence of two equivalents of NEt3, afforded the dichloro derivatives M(η5-C5H4SiClMe2)2Cl2 [M=Ti (2a), Hf (2c)]. Compounds 2a and 2c react with a

  的二甲硅烷基化的环戊二烯的C反应5 ħ 4（SiClMe 2）（森达3）用的HfCl 4，在庚烷中，得到单环戊二烯基络合物的Hf（η 5 -C 5 H ^ 4 SiClMe 2）氯3（1C）。的C两个当量的另外5 ħ 5（SiClMe 2）到的MC1中的溶液4在回流下和在网的两个当量的存在下，在甲苯3，得到二氯衍生物M（η 5 -C 5 H ^ 4 SiClMe2）2 Cl 2 [M ＝ Ti（2a），Hf（2c）]。化合物2A和2C与水与SiCl键的选择性水解的化学计量量的反应，得到四甲基二硅氧烷桥连络合物diciclopentadienylμ（η 5 -C 5 H ^ 4）森达2 OSiMe 2（η 5 -C 5 H ^ 4）} Cl 2 [M ＝ Ti（3a），Hf（3c）]。三氯金属的化合物反应M（η 5 -C 5 H ^ 4SiClMe 2）氯3与铊（1,3-吨卜2 ç 5 ħ
• Synthesis of sandwich and half-sandwich complexes of Ti, Zr and Hf containing η5-C5H4SiMe2Cl ligand. Molecular structure of [TiCl2(μ-OSiMe2-η5-C5H4)]2
  作者：Andrew V. Churakov、Dmitry A. Lemenovskii、Ludmila G. Kuz'mina

  DOI：10.1016/0022-328x(94)05241-3

  日期：1995.3

  Reactions of (C(5)H(4)SiMe(3))SiMe(2)Cl (1) and (mu-SiMe(2)C(5)H(4))(2) (2) with Ti, Zr and Hf tetrachlorides lead to the complexes M(eta(5)-C(5)H(4)SiMe(2)Cl)Cl-3 (M = Ti, 3a; Zr, 3b; Hf, 3c). Treatment of 3a with cyclopentadienyl thallium affords Ti(eta(5)-C5H5)(eta(5)- C(5)H(4)SiMe(2)Cl)Cl-2 (4). Dimeric oxo-derivative [TiCl2(mu-OSiMe(2)-eta(5)-C5H4)](2) (5) was prepared by slow hydrolysis of 3a. Structure of 5 was determined by X-ray diffraction.
• Silyl and siloxanediyl cyclopentadienyl titanium and zirconium complexes: synthesis and reactivity. X-ray molecular structure of [Zr{η5-C5H4SiMe2(μ-OH)} (μ-Cl)Cl2]2
  作者：Santiago Ciruelos、Tomás Cuenca、Rafael Gómez、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1016/s0277-5387(97)00491-9

  日期：1998.1

  Chloro(dimethyl)silyl-eta(5)-cyclopentadienyl group 4 metal complexes of the type [M(mu(5)-C5H4SiMe2 Cl)Cl-3] (M = Ti 1, Zr 2) react with thallium salts Tl(C5H4R) (R = H, SiMe3) to give mixed dicyclopentadienyl derivatives [M(eta(5)-C5H4R)(eta(5)-C5H4SiMe2Cl)Cl-2], (M = Ti, R = H 3, R = SiMe3 4; M = Zr, R = H 5, R = SiMe3 6) in high yield. Hydrolysis of complexes 3 and 4 affords the dinuclear complexes [Ti(eta(5)-C5H4R)Cl-2](2)mu(5)-[(eta(5)-C5H4SiMe2)(2)O]} (R = H 7, R = SiMe3 8) containing a siloxanyl bridge, by elimination of two equivalents of HCl. Reactions of complexes 1 with hydroxo containing reagents such as anhydrous LiOH and SiPh2(OH)(2) give the derivatives [Ti(eta(5)-C5H4SiMe2Cl)Cl-2](2)(mu-O)], 9 and Ti[mu-(mu(5)-C5H4SiMe2OSiPh2-eta(1)-O)]Cl-2, 10 identified by analytical, spectrometric and spectroscopic data. Treatment of analogous complex 2 with water produces the dimeric monocyclopentadienyl zirconium trichloride adduct [Zr(eta(5)-C5H4SiMe2OH)Cl-3](2), 11. Compound 11 has been characterized by X-ray crystallography. (C) 1998 Elsevier Science Ltd. All rights reserved.
• 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.