((1-trimethylsilyl)-.eta(5)-indenyl)(η(5)-C5H5)ZrCl2 | 197309-48-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: ((1-trimethylsilyl)-.eta(5)-indenyl)(η(5)-C5H5)ZrCl2
• 英文别名: cyclopenta-1,3-diene;dichlorozirconium(2+);inden-1-id-1-yl(trimethyl)silane
• CAS: 197309-48-1
• 化学式: C₁₇H₂₀Cl₂SiZr
• 分子量: 414.561
• InChiKey: ABKKINUHWUJQLD-UHFFFAOYSA-L

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：

  ((1-trimethylsilyl)-.eta(5)-indenyl)(η(5)-C5H5)ZrCl2 、 氢气 在 platinum(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 以58%的产率得到(η(5)-1-(trimethylsilyl)-4,5,6,7-tetrahydroindenyl)(η(5)-C5H5)ZrCl2
  参考文献：
  名称：

  Electrophile-Functionalized Metallocene Intermediates. Application in the Diastereoselective Synthesis of a Tetramethyldisiloxane-Bridged C₂-Symmetric ansa-Zirconocene Dibromide

  摘要：

  The reactivity of group 4 zirconocene dichlorides incorporating (1-trimethylsilyl)-eta(5)-indenyl (Me(3)SiInd) and eta(5)-1-(trimethylsilyl)-4,5,6,7-tetrahydro (Me3SiTHI) ligands toward boron tribromide was investigated. Whereas the reaction of (Me(3)SiInd)CpZrCl2 (1) with BBr3 in CH2Cl2 immediately cleaved the indenyl ligand from the metal, (Me3SiTHI)CpZrCl2 (3) reacted with BBr3 in CH2Cl2 at 70 degrees C for 2 days to obtain [1-(BrSiMe2)THI]CpZrBr2 (6) in 49% yield. The reaction of (Me(3)SiInd)Li (2 equiv) with ZrCl4(THF)(2) afforded pure rac-(Me(3)SiInd)(2)ZrCl2 (2) in 60% yield. Hydrogenation of (2) (50 bar, PtO2 catalyst) afforded rac-(Me3SiTHI)(2)ZrCl2 (4) in 81% yield. Single-crystal X-ray diffraction analysis of 4 showed that the Zr atom Lies on a crystallographic C-2 axis with the C4H8 annelated rings projecting into the ZrCl2 hemisphere of the pseudotetrahedral coordination environment. The reaction of 4 with MeLi in toluene afforded rac-(Me3SiTHI)(2)ZrMe2 (5) in 62% yield. H-1 NMR and C-13 NMR analysis confirmed the rac assignment for 5. Treatment of 4 with BBr3 in CH2Cl2 at 70 degrees C for 2 days afforded rac-[1-(BrMe2Si)THI](2)ZrBr2 (7) in 78% yield. The reaction of 7 with moisture in ambient air gave the ansa-metallocene rac-[mu-O-(1-Me2SiTKI)(2)]ZrBr2 (8) in 97% yield. In solution, 8 showed time-averaged C-2 symmetry (H-1 NMR); however, single-crystal X-ray diffraction analysis showed that 8 adopts an asymmetric conformation in which only one of the C4H8 annelated rings projects into the ZrCl2 coordination hemisphere. Neither 4 nor 8 served as a precatalyst for alumoxane-cocatalyzed, homogeneous propylene polymerization.

  DOI：

  10.1021/om9903339
• 作为产物：
  描述：

  cyclopentadienylzirconium trichloride 、 lithium,inden-1-id-1-yl(trimethyl)silane 以 四氢呋喃 为溶剂， 以73%的产率得到((1-trimethylsilyl)-.eta(5)-indenyl)(η(5)-C5H5)ZrCl2
  参考文献：
  名称：

  Electrophile-Functionalized Metallocene Intermediates. Application in the Diastereoselective Synthesis of a Tetramethyldisiloxane-Bridged C₂-Symmetric ansa-Zirconocene Dibromide

  摘要：

  The reactivity of group 4 zirconocene dichlorides incorporating (1-trimethylsilyl)-eta(5)-indenyl (Me(3)SiInd) and eta(5)-1-(trimethylsilyl)-4,5,6,7-tetrahydro (Me3SiTHI) ligands toward boron tribromide was investigated. Whereas the reaction of (Me(3)SiInd)CpZrCl2 (1) with BBr3 in CH2Cl2 immediately cleaved the indenyl ligand from the metal, (Me3SiTHI)CpZrCl2 (3) reacted with BBr3 in CH2Cl2 at 70 degrees C for 2 days to obtain [1-(BrSiMe2)THI]CpZrBr2 (6) in 49% yield. The reaction of (Me(3)SiInd)Li (2 equiv) with ZrCl4(THF)(2) afforded pure rac-(Me(3)SiInd)(2)ZrCl2 (2) in 60% yield. Hydrogenation of (2) (50 bar, PtO2 catalyst) afforded rac-(Me3SiTHI)(2)ZrCl2 (4) in 81% yield. Single-crystal X-ray diffraction analysis of 4 showed that the Zr atom Lies on a crystallographic C-2 axis with the C4H8 annelated rings projecting into the ZrCl2 hemisphere of the pseudotetrahedral coordination environment. The reaction of 4 with MeLi in toluene afforded rac-(Me3SiTHI)(2)ZrMe2 (5) in 62% yield. H-1 NMR and C-13 NMR analysis confirmed the rac assignment for 5. Treatment of 4 with BBr3 in CH2Cl2 at 70 degrees C for 2 days afforded rac-[1-(BrMe2Si)THI](2)ZrBr2 (7) in 78% yield. The reaction of 7 with moisture in ambient air gave the ansa-metallocene rac-[mu-O-(1-Me2SiTKI)(2)]ZrBr2 (8) in 97% yield. In solution, 8 showed time-averaged C-2 symmetry (H-1 NMR); however, single-crystal X-ray diffraction analysis showed that 8 adopts an asymmetric conformation in which only one of the C4H8 annelated rings projects into the ZrCl2 coordination hemisphere. Neither 4 nor 8 served as a precatalyst for alumoxane-cocatalyzed, homogeneous propylene polymerization.

  DOI：

  10.1021/om9903339