1,1'-bis(t-butyldimethylsilyl)zirconocene dichloride | 181650-82-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1,1'-bis(t-butyldimethylsilyl)zirconocene dichloride
• 英文别名: Zr(η5-C5H4SiMe2(t-Bu))2Cl2；zirconium (η5-tert-butyldimethylsilylcyclopentadienyl)2Cl2；Tert-butyl-cyclopenta-2,4-dien-1-yl-dimethylsilane;zirconium(4+);dichloride
• CAS: 181650-82-8
• 化学式: C₂₂H₃₈Cl₂Si₂Zr
• 分子量: 520.845
• InChiKey: XXJTWRCJIDMMIJ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  1,1'-bis(t-butyldimethylsilyl)zirconocene dichloride 、 苄基氯化镁 以 四氢呋喃 为溶剂， 以65%的产率得到Zr(η5-C5H4SiMe2(t-Bu))(CH2C6H5)2
  参考文献：
  名称：

  tert-Butylsilylcyclopentadienyl Group 4 metal complexes

  摘要：

  New Group 4 metal t-butyldimethylsilyleyclopentadienyl complexes [MCpCp'Cl-2] (Cp = eta(5)-C5H5 : Cp' = eta(5)'-C5H4SiMe2',Bu; M = Ti 4, Zr 5, Hf 6) were prepared by reaction of 1 equiv. of the lithium (2) and thallium (3) salts of t-butyldimethylsilylcyclopentadiene I with the monocyclopentadienyl complexes [MCpCl3. DME] (M = Zr, Hf) and [TiCpCl3], respectively, A similar reaction using ZrCl4(THF)2 and HfCl4 with 2 equiv. of the lithium salt 2 gave the symmetric [MCp2Cl2] (M = Zr 7, Hf8) rnetallocenes. Alkylation of these compounds with 2 equiv. of MgRCl (R = Me. CH2Ph) and Li(CH2CMe2Ph) afforded the dialkyl complexes [MCpCp'R-2] (R = Me, M = Zr 9, Hf 10: R = CH2Ph. M = Ti 11. Zr 12. Hf 13). [ZrCp2(CH2Ph):] 14 and [ZrCpCp'(CH2CMe2Ph)(2)] 17, A Similar reaction of 5 with 1 equiv. of Mg(CH2Ph)Cl gave the monobenzyl compound [ZrCpCp'Cl(CH2Ph)] (15), Hydrolysis of 15 with a stoichiometric amount of water afforded the dinuclear mu-oxo compound [(ZrCpCp'Cl)(2)(mu-O)] (16). All of the new complexes reported were characterized by elemental analysis and H-1 and C-13 NMR spectroscopy and the molecular structures of 4 and 16 were determined by X-ray diffraction methods. Ethylene polymerization activities were measured for compounds 4-7. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01446-9
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 lithium tert-butyldimethylsilylcyclopentadienyl 以 四氢呋喃 为溶剂， 以80%的产率得到1,1'-bis(t-butyldimethylsilyl)zirconocene dichloride
  参考文献：
  名称：

  Influence of the Departing Group on the Electrophilic Cleavage of Silicon−Carbon Bonds Adjacent to Zirconocene Dichloride. Preparation of Electrophile-Functionalized Zirconocene Dibromides

  摘要：

  (EtMe2SiC5H4)CpZrCl2 (5) reacts with BBr3 in 1,2-dichloroethane (reflux, 24 h) to afford a 4:1 mixture of (EtMeBrSiC5H4)CpZrBr2 (10) and (BrMe2SiC5H4)CpZrBr2 (11) in a nearly quantitative conversion. Similarly, ((BuMe2SiC5H4)-Bu-t)CpZrCl2 (6) reacts with BBr3 to afford a 15:1 mixture of ((BuMeBrSiC5H4)-Bu-t)CpZrBr2 (13) and 11. The product 11 is obtained independently by treating (Me3SiC5H4)CpZrCl2 (12) with BBr3. In contrast, Si-Ph bonds are cleaved with complete selectivity in the presence of Si-Me groups. (PhMe2SiC5H4)(2)-ZrCl2 (8) reacts with excess BCl3 in dichloromethane (reflux, 15 h) to afford (ClMe2SiC5H4)(2)-ZrCl2 (14) in 72% yield. (Ph2MeSiC5H4)(2)ZrCl2 (9) reacts with excess BBr3 in 1,2-dichloroethane (reflux, 15 h) to afford (Br2MeSiC5H4)(2)ZrBr2 (15) in 79% yield. Complexes 9 and 15 were analyzed by single-crystal X-ray diffraction. Crystalline 9 adopts a pseudo-C-2 conformation in which the face of the Ph group of one ligand shows a weak interaction with a C-H bond of the other ligand. Crystalline 15 also adopts a pseudo-C-2 conformation, in which the SiBr2 groups are directed away from the ZrBr2 group.

  DOI：

  10.1021/om0005452