| 353487-92-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• CAS: 353487-92-0
• 化学式: C₂₂H₃₈N₂Si₂Zr
• 分子量: 477.952
• InChiKey: NBIFBKBOZOWKAB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  、 三乙胺盐酸盐 以 二氯甲烷 为溶剂， 以91%的产率得到bis[(μ-dimethylsilyl)(η5-cyclopentadienyl)]dichlorozirconium
  参考文献：
  名称：

  Ring-Opening Polymerization Behavior of ansa- and Spirocyclic ansa-Zirconocene Complexes

  摘要：

  Attempts to develop a ring-opening polymerization (ROP) approach to polymeric zirconocene complexes are reported. A new silicon-bridged [1][1] zirconocenophane, (SiMe2)(2)(eta (5)-C5H3)(2)Zr(NEt2)(2) (3a), was synthesized by reaction of Zr(NEt2)(4) with (C5H4)(2)(SiMe2)(2) (4) Single-crystal X-ray diffraction revealed a highly tilted structure with an angle of 73.1(4)degrees, a significant increase over the untethered compound (eta (5)-MeC5H4)(2)ZrCl2 (2), which possesses a tilt angle of 54.2 degrees. This and the related compounds (SiMe2)(eta (5)-C5H4)(2)MCl2 (1a, M = Ti; Ib, M = Zr) and (SiMe2)(2)(eta (5)-C5H3)(2)ZrCl2 (3b) were tested for transition-metal catalyzed ROP behavior in the presence of Pt(0) catalysts but were found to be inactive. The novel spirocyclic silacyclobutane-bridged monomer (CH2)(3)Si(eta (5)-C5H4)(2)ZrCl2 (7b) was prepared via a "fly trap" amine elimination reaction between cyclotrimethylenedicyclopentadienylsilane (8) and Zr(NMe2)(4); this initially yielded (CH2)(3)Si(eta (5)-C5H4)(2)Zr(NMe2)(2) (7a), which was converted to 7b by reaction with a slight excess of Me3SiCl. 7a and 7b were characterized by Si-29, C-13, and H-1 NMR spectroscopy and mass spectrometry as well as single-crystal X-ray diffraction. Both showed moderate tilt angles (61.7(2)degrees and 59.69(7)degrees, respectively) as well as highly strained silacyclobutane rings with C-Si-C bond angles of 79.7(2)degrees and 80.64(10)4 respectively. Transition-metal-catalyzed ROP of 7b led to the formation of the polycarbosilane [(CH2)(3)Si(eta (5)-C5H4)(2)ZrCl2](n) (10). Both the soluble and insoluble fractions of 10 were characterized by CP-MAS Si-29 and C-13 NMR, and the soluble, oligomeric fraction was further characterized by solution Si-29, C-13,and H-1 NMR. Complexes 7a, 7b, and polyzirconocene 10 were found to exhibit moderate activity as ethylene polymerization catalysts.

  DOI：

  10.1021/om001023p
• 作为产物：
  描述：

  Zr(NEt2)4 、 2,2,8,8-tetramethyl-2,8-disilatricyclo{7.3.0.0(3.7)}dodeca-3,5,9,11-tetraene 以 甲苯 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  Ring-Opening Polymerization Behavior of ansa- and Spirocyclic ansa-Zirconocene Complexes

  摘要：

  Attempts to develop a ring-opening polymerization (ROP) approach to polymeric zirconocene complexes are reported. A new silicon-bridged [1][1] zirconocenophane, (SiMe2)(2)(eta (5)-C5H3)(2)Zr(NEt2)(2) (3a), was synthesized by reaction of Zr(NEt2)(4) with (C5H4)(2)(SiMe2)(2) (4) Single-crystal X-ray diffraction revealed a highly tilted structure with an angle of 73.1(4)degrees, a significant increase over the untethered compound (eta (5)-MeC5H4)(2)ZrCl2 (2), which possesses a tilt angle of 54.2 degrees. This and the related compounds (SiMe2)(eta (5)-C5H4)(2)MCl2 (1a, M = Ti; Ib, M = Zr) and (SiMe2)(2)(eta (5)-C5H3)(2)ZrCl2 (3b) were tested for transition-metal catalyzed ROP behavior in the presence of Pt(0) catalysts but were found to be inactive. The novel spirocyclic silacyclobutane-bridged monomer (CH2)(3)Si(eta (5)-C5H4)(2)ZrCl2 (7b) was prepared via a "fly trap" amine elimination reaction between cyclotrimethylenedicyclopentadienylsilane (8) and Zr(NMe2)(4); this initially yielded (CH2)(3)Si(eta (5)-C5H4)(2)Zr(NMe2)(2) (7a), which was converted to 7b by reaction with a slight excess of Me3SiCl. 7a and 7b were characterized by Si-29, C-13, and H-1 NMR spectroscopy and mass spectrometry as well as single-crystal X-ray diffraction. Both showed moderate tilt angles (61.7(2)degrees and 59.69(7)degrees, respectively) as well as highly strained silacyclobutane rings with C-Si-C bond angles of 79.7(2)degrees and 80.64(10)4 respectively. Transition-metal-catalyzed ROP of 7b led to the formation of the polycarbosilane [(CH2)(3)Si(eta (5)-C5H4)(2)ZrCl2](n) (10). Both the soluble and insoluble fractions of 10 were characterized by CP-MAS Si-29 and C-13 NMR, and the soluble, oligomeric fraction was further characterized by solution Si-29, C-13,and H-1 NMR. Complexes 7a, 7b, and polyzirconocene 10 were found to exhibit moderate activity as ethylene polymerization catalysts.

  DOI：

  10.1021/om001023p