(Cp-1,2,3-Me3)2ZrCl2 | 119445-93-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: (Cp-1,2,3-Me3)2ZrCl2
• 英文别名: bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride；dichlorozirconium(2+);1,2,5-trimethylcyclopenta-1,3-diene
• CAS: 119445-93-1
• 化学式: C₁₆H₂₂Cl₂Zr
• 分子量: 376.481
• InChiKey: RCRZQFJIAXYAEJ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.33
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• 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：

  (Cp-1,2,3-Me3)2ZrCl2 、 二(三甲基甲硅烷基)乙炔 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到[(η⁵-1,2,3-C₅H₂Me₃)₂Zr(η²-bis(trimethylsilyl)acetylene)]
  参考文献：
  名称：

  Methyl-Substituted Zirconocene−Bis(trimethylsilyl)acetylene Complexes (C₅H_5-nMe_n)₂Zr(η²-Me₃SiC⋮CSiMe₃) (n = 2−5)

  摘要：

  The (C(5)H(5-n)Me(n))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (n = 2-5; 1,3-dimethyl, 1,2,3-trimethyl) (2C-F) complexes were prepared by the reduction of corresponding zirconocene dichlorides with magnesium in THF in the presence of bis(trimethylsilyl)acetylene (BTMSA). All of them are stable in the absence of THF. Crystal structures of (C(5)HMe(4))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2E) and (C(5)Me(5))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2F) and ofthe analogous titanium complexes are isomorphous. The red shift of the nu(C=C) vibration and the downfield shift of C-13 delta(C=C) indicate that BTMSA in 2C-F is more strongly coordinated than in analogous titanocene complexes. The nonisolated complex (C(5)H(4)Me)(2)Zr[eta(2)-C-2(SiMe(3))(2)](THF) (2B . THF) rearranges after the loss of THF to give the dimer [(eta(5)-C(5)H(4)Me)(eta(1)-C(SiMe(3))=CH(SiMe(3))Zr(mu-eta(1):eta(5)-C(5)H(3)Me)](2) (3B).

  DOI：

  10.1021/om960184j
• 作为产物：
  描述：

  氯化锆(IV) 在 C₅H₃Me₃ 、 BuLi 、 HCl 作用下， 以 正己烷 、 水 、 甲苯 为溶剂， 以36%的产率得到(Cp-1,2,3-Me3)2ZrCl2
  参考文献：
  名称：

  Methyl-Substituted Zirconocene−Bis(trimethylsilyl)acetylene Complexes (C₅H_5-nMe_n)₂Zr(η²-Me₃SiC⋮CSiMe₃) (n = 2−5)

  摘要：

  The (C(5)H(5-n)Me(n))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (n = 2-5; 1,3-dimethyl, 1,2,3-trimethyl) (2C-F) complexes were prepared by the reduction of corresponding zirconocene dichlorides with magnesium in THF in the presence of bis(trimethylsilyl)acetylene (BTMSA). All of them are stable in the absence of THF. Crystal structures of (C(5)HMe(4))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2E) and (C(5)Me(5))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2F) and ofthe analogous titanium complexes are isomorphous. The red shift of the nu(C=C) vibration and the downfield shift of C-13 delta(C=C) indicate that BTMSA in 2C-F is more strongly coordinated than in analogous titanocene complexes. The nonisolated complex (C(5)H(4)Me)(2)Zr[eta(2)-C-2(SiMe(3))(2)](THF) (2B . THF) rearranges after the loss of THF to give the dimer [(eta(5)-C(5)H(4)Me)(eta(1)-C(SiMe(3))=CH(SiMe(3))Zr(mu-eta(1):eta(5)-C(5)H(3)Me)](2) (3B).

  DOI：

  10.1021/om960184j

文献信息

• 1H-, 13C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: effect of the ligand structure on the formation of active intermediates and polymerization kinetics
  作者：Konstantin P Bryliakov、Nina V Semikolenova、Dmitrii V Yudaev、Vladimir A Zakharov、Hans H Brintzinger、Martin Ystenes、Erling Rytter、Evgenii P Talsi

  DOI：10.1016/s0022-328x(03)00443-1

  日期：2003.10

  Using H-1- and C-13-NMR spectroscopies, cationic intermediates formed by activation of L2ZrCl2 with methylaluminoxane (MAO) in toluene were monitored at Al/Zr ratios from 50 to 1000 (L-2 are various cyclopentadienyl (Cp), indenyl (Ind) and fluorenyl (Flu) ligands). The following catalysts were studied: (Cp-R)(2)ZrCl2 (R = Me, 1,2-Me2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, Me-5, n-Bu, t-Bu), rac-ethanediyl(Ind)(2)ZrCl2, rac-Me2Si(Ind)(2)ZrCl2, rac-Me2Si(1-Ind-2-Me)(2)ZrCl2, rac-ethanediyl(1-Ind-4,5,6,7-H-4)(2)ZrCl2, (Ind-2Me)(2)ZrCl2, Me2C(CP)(Flu)ZrCl2, Me2C(Cp-3-Me)(Flu)ZrCl2 and Me2Si(Flu)(2)ZrCl2- Correlations between spectroscopic and ethene polymerization data for catalysts (Cp-R)(2)ZrCl2/MAO (R = H, Me, 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, Me-5, n -Bu, t-Bu) and rac-Me2Si(Ind)(2)ZrCl2 were established. The catalysts (Cp-R)(2)ZrCl2/AlMe3/CPh3+B(C6F5)(4)(-) (R= Me, 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4, n -Bu, t -Bu) were also studied for comparison of spectroscopic and polymerization data with MAO-based systems. Complexes of type (Cp-R)(2)ZrMe+ <-- Me- -Al equivalent to MAO (IV) with different [Me-MAO](-) counteranions have been identified in the (Cp-R)(2)ZrCl2/MAO (R = H-Bu, t-Bu) systems at low Al/Zr ratios (50-200). At Al/Zr ratios of 500-1000, the complex [L2Zr(mu-Me)(2)AlMe2](+)[Me-MAO](-) (HI) dominates in all MAO-based reaction systems studied. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr = 200 - 1000) for the systems (Cp-R)(2)ZrCl2/MAO (R = H, Me, n -Bu, t -Bu), while it is virtually constant in the same range of Al/Zr ratios for the catalytic systems (Cp-R)(2)ZrCl2/MAO (R = 1,2-Me-2, 1,2,3-Me-3, 1,2,4-Me-3, Me-4) and rac-Me2Si(Ind)(2)ZrCl2/MAO. The data obtained are interpreted on assumption that complex III is the main precursor of the active centers of polymerization in MAO-based systems. (C) 2003 Elsevier Science B.V. All rights reserved.
• Methyl-Substituted Zirconocene−Bis(trimethylsilyl)acetylene Complexes (C₅H₅_-<i>_n</i>Me<i>_n</i>)₂Zr(η²-Me₃SiC⋮CSiMe₃) (<i>n</i> = 2−5)
  作者：Jörg Hiller、Ulf Thewalt、Miroslav Polášek、Lidmila Petrusová、Vojtech Varga、Petr Sedmera、Karel Mach

  DOI：10.1021/om960184j

  日期：1996.8.20

  The (C(5)H(5-n)Me(n))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (n = 2-5; 1,3-dimethyl, 1,2,3-trimethyl) (2C-F) complexes were prepared by the reduction of corresponding zirconocene dichlorides with magnesium in THF in the presence of bis(trimethylsilyl)acetylene (BTMSA). All of them are stable in the absence of THF. Crystal structures of (C(5)HMe(4))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2E) and (C(5)Me(5))(2)Zr[eta(2)-C-2(SiMe(3))(2)] (2F) and ofthe analogous titanium complexes are isomorphous. The red shift of the nu(C=C) vibration and the downfield shift of C-13 delta(C=C) indicate that BTMSA in 2C-F is more strongly coordinated than in analogous titanocene complexes. The nonisolated complex (C(5)H(4)Me)(2)Zr[eta(2)-C-2(SiMe(3))(2)](THF) (2B . THF) rearranges after the loss of THF to give the dimer [(eta(5)-C(5)H(4)Me)(eta(1)-C(SiMe(3))=CH(SiMe(3))Zr(mu-eta(1):eta(5)-C(5)H(3)Me)](2) (3B).