(Cp-t-Bu)2ZrClMe | 159666-79-2

• 英文名称: (Cp-t-Bu)2ZrClMe
• CAS: 159666-79-2
• 化学式: C₁₉H₂₉ClZr
• 分子量: 384.116
• InChiKey: KKDVVSANWMHYNO-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：

  (Cp-t-Bu)2ZrClMe 、 甲苄基溴 在 Li 作用下， 以 乙醚 为溶剂， 以28%的产率得到
  参考文献：
  名称：

  Legrand, Corinne; Meunier, Philippe; Petersen, Jeffrey L., Organometallics, 1995, vol. 14, # 1, p. 162 - 169

  摘要：

  DOI：
• 作为产物：
  描述：

  bis(tert-butylcyclopentadienyl)zirconium dichloride 、 三甲基铝 以 氘代甲苯 为溶剂， 生成 (Cp-t-Bu)2ZrClMe
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(03)00443-1

文献信息

• Alkyl exchange between aluminum trialkyls and zirconocene dichloride complexes — a measure of electron densities at the Zr center
  作者：Stefan Beck、Hans H. Brintzinger

  DOI：10.1016/s0020-1693(97)05871-4

  日期：1998.4

  Equilibrium constants have been determined for the formation of 15 different zirconocene monomethyl monochloro complexes from the respective dichloride complexes and Al-2(CH3)(6). The results indicate chat the tendency of a particular zirconocene complex to exchange a chloride against a methyl ligand is a measure for the electron deficiency at its Zr center. The results indicate particularly low electron densities for complexes with indenyl instead of cyclopentadienyl ligands, especially for those containing a dimethylsilyl bridge. Only one methyl group is transferred to a zirconocene dichloride even by a large excess of Al-2(CH3)(6), while the uptake of two alkyl groups, followed by alkane evolution, is observed with triethyl and triisobutyl aluminum. (C) 1998 Elsevier Science S.A.