1,1'-bis(methyldiphenylsilyl)zirconocene dichloride | 302342-98-9

• 英文名称: 1,1'-bis(methyldiphenylsilyl)zirconocene dichloride
• CAS: 302342-98-9
• 化学式: C₃₆H₃₄Cl₂Si₂Zr
• 分子量: 684.967
• InChiKey: NAJJKAOGDKZKGE-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：
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• 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(methyldiphenylsilyl)zirconocene dichloride 、 三溴化硼 以 1,2-二氯乙烷 为溶剂， 以79%的产率得到1,1'-bis(methyldibromosilyl)zirconocene dibromide
  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
• 作为产物：
  描述：

  zirconium tetrachloride bis(tetrahydrofuran) complex 、 以 甲苯 为溶剂， 以60%的产率得到1,1'-bis(methyldiphenylsilyl)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