(3,5-Me2-pyrazolyl)2CHSi(p-tolyl)3 | 1004983-13-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3,5-Me2-pyrazolyl)2CHSi(p-tolyl)3
• 英文别名: Bis(3,5-dimethylpyrazol-1-yl)methyl-tris(4-methylphenyl)silane；bis(3,5-dimethylpyrazol-1-yl)methyl-tris(4-methylphenyl)silane
• CAS: 1004983-13-4
• 化学式: C₃₂H₃₆N₄Si
• 分子量: 504.75
• InChiKey: YBGVDVMSBHVLOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  37
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3,5-Me2-pyrazolyl)2CHSi(p-tolyl)3 以 乙醚 、 二氯甲烷-D2 为溶剂， 生成 [((3,5-Me2-pyrazolyl)2CHSi(p-tolyl)3)Pd(CO)(COCH3)][B(C6F5)4]
  参考文献：
  名称：

  Mechanism of Ethylene Oligomerization by a Cationic Palladium(II) Alkyl Complex that Contains a (3,5-Me₂-pyrazolyl)₂CHSi(p-tolyl)₃) Ligand

  摘要：

  The reactivity of the ethylene oligomerization catalyst (N boolean AND N)Pd(Me)(ethylene)(+) (5), which contains a silyl-capped bis-pyrazolyl methane ligand (N boolean AND N) = (3,5-Me-2-pyrazolyl)(CHSi)-C-2(p-tolyl)3 (1)) was investigated. The reaction of (N boolean AND N)PdMeCl (3) with Li[B(C6F5)4] and ethylene in CH2Cl2 generates 5. Complex 5 undergoes ethylene insertion at -10 degrees C with a rate constant of k(insert.Me) = 3.3 (3) x 10(-3) s(-1). Complex 5 catalytically oligomerizes ethylene to branched C-6-C-20 internal olefins (-10 to 20 degrees C; 2.7-30 atm ethylene). NMR studies show that an equilibrium mixture of base-free beta-agostic secondary alkyl (N boolean AND N)PdR+ species (8) and ethylene adducts (N boolean AND N)Pd(R)(ethylene)+ (9) is present under oligomerization conditions. Complex 9 decomposes to NO at 20 degrees C, resulting in catalyst decomposition. (N boolean AND N)Pd(R)(L)+ species containing R groups that can function as internal donors (either eta(2)-acyl or agostic beta-H) undergo a dynamic process that exchanges the two pz* rings and are thermally unstable. It is proposed that catalyst decomposition and pz* exchange both involve initial coordination of the internal donor to generate a configurationally labile five-coordinate intermediate, which isomerizes, resulting in pz* site exchange or displacement of one arm of the N boolean AND N ligand.

  DOI：

  10.1021/om7007698