cyclotrimethylenedicyclopentadienylsilane | 353487-89-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: cyclotrimethylenedicyclopentadienylsilane
• 英文别名: 1,1-dicyclopentadienyl-1-silacyclobutane；1,1-Di(cyclopenta-2,4-dien-1-yl)siletane
• CAS: 353487-89-5
• 化学式: C₁₃H₁₆Si
• 分子量: 200.356
• InChiKey: ZSKMSPUXQKHSAY-UHFFFAOYSA-N

物化性质

• 沸点：
  273.4±9.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.83
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  3.0
• 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：
  0

反应信息

• 作为反应物：
  描述：

  cyclotrimethylenedicyclopentadienylsilane 、 四氯化钛 在 n-butyllithium 作用下， 以 乙醚 、 正己烷 为溶剂， 以38%的产率得到dichloro(η5:η5-1,1-dicyclopentadienyl-1-silacyclobutane(2-))titanium(IV)
  参考文献：
  名称：

  Syntheses, Structural Characterizations, and Catalytic Behavior of ansa-Metallocene Complexes Derived from 1,1-Dicyclopentadienyl-1-silacycloalkanes

  摘要：

  1,1-Dicyclopentadienyl-1-silacycloalkanes (2) were prepared by condensation of cyclopentadiene with appropriate 1,1-dichloro-1-silacycloalkanes [(cycl)SiCl2 (1); cycl = CnH2n, n = 3, 4, 5]. Dilithium salts of 2 were subsequently transformed into the corresponding ansa-metallocene complexes [ {eta:(5eta5)-Cp-2-(cycl)Si}MCl2] (M = Ti (3), Zr (4), Hf (5)). The molecular structures of 3b, 3c, 4b, and 4c were determined by X-ray crystallography. As a result of the formation of the siladicyclopentadienyl ring, the metal atoms in 3-5 exhibit distorted tetrahedral configurations with the two chloride atoms. DFT calculations established that the size of the bridge ring influenced the catalytic activity. Thus, the catalytic activity of the ansa-titanocene complexes was remarkably enhanced by the silacycloalkyl bridge due to their increased conformational stability (14 x 10(3) kg PE mol(cat)(-1) h(-1) for 3c). In addition, polyethylenes with high molecular weight such as M-w = (1.3-2.6) x 10(6) (M-w/M-n = 1.6-2.0 by GPC) were obtained with 3.

  DOI：

  10.1021/om030287j

文献信息

• Ring-Opening Polymerization Behavior of <i>ansa</i>- and Spirocyclic <i>ansa</i>-Zirconocene Complexes
  作者：Timothy J. Peckham、Paul Nguyen、Sara C. Bourke、Qinyan Wang、Daryll G. Harrison、Peter Zoricak、Charles Russell、Louise M. Liable-Sands、Arnold L. Rheingold、Alan J. Lough、Ian Manners

  DOI：10.1021/om001023p

  日期：2001.7.1

  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.