dimethyl-bis(2-methylcyclopenta[a]naphthalen-3-id-3-yl)silane;methyl(phenyl)azanide;zirconium(4+) | 299945-18-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: dimethyl-bis(2-methylcyclopenta[a]naphthalen-3-id-3-yl)silane;methyl(phenyl)azanide;zirconium(4+)
• CAS: 299945-18-9
• 化学式: C₄₄H₄₂N₂SiZr
• 分子量: 718.14
• InChiKey: UOIPRYWOCPKJIX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.82
• 重原子数：
  48
• 可旋转键数：
  2
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  methyl(phenyl)azanide;oxolane;zirconium(4+);dichloride 、 以 乙醚 为溶剂， 生成 dimethyl-bis(2-methylcyclopenta[a]naphthalen-3-id-3-yl)silane;methyl(phenyl)azanide;zirconium(4+) 、
  参考文献：
  名称：

  Chelate-Controlled Synthesis of Racemic ansa-Zirconocenes

  摘要：

  The reaction of Zr{PhN(CH2)(3)NPh}Cl-2(THF)(2) (5) with lithium ansa-bis-indenyl reagents Li-2[XBI]-(Et2O) (XBI = (1-indenyl)(2)SiMe2 (SBI, 7a), (2-methyl-1-indenyl)(2)SiMe2 (MSBI, 7b), (2-methyl-4,5-benz-1-indenyl)(2)SiMe2 (MBSBI, 7c), (2-methyl-4-phenyl-1-indenyl)(2)SiMe2 (MPSBI, 7d), and 1,2-(1-indenyl)(2)ethane (EBI, 7e)) affords rac-(XBI)Zr{PhN(CH2)(3)NPh} (8a-e) in high yield. The meso isomers were not detected by H-1 NMR. X-ray crystallographic studies show that the Zr{PhN(CH2)(3)NPh) rings in 5, 8a, 8c, and (C5H5)(2)-Zr{PhN(CH2)(3)NPh} (10) adopt twist conformations that position the N-Ph groups on opposite sides of the N-Zr-N plane. This conformation complements the metallocene structures of rac-8a-e but would destabilize the corresponding meso isomers. It is proposed that the Zr{PhN(CH2)(3)NPh} ring adopts a similar twist conformation in the stereodetermining transition state for addition of the second indenyl ring in these reactions, which leads to a preference for rac products. The results of metallocene syntheses from other Zr amide precursors support this proposal. 8a-e are converted to the corresponding rac-(XBI)ZrCl2 complexes (9a-e) by reaction with HCl.

  DOI：

  10.1021/ja046629+