(η(5)-EtMe2SiC5H4)(η(5)-C5H5)ZrCl2 | 320350-29-6

• 英文名称: (η(5)-EtMe2SiC5H4)(η(5)-C5H5)ZrCl2
• CAS: 320350-29-6
• 化学式: C₁₄H₂₀Cl₂SiZr
• 分子量: 378.528
• InChiKey: NZQQUVXBFJQPKM-UHFFFAOYSA-L

反应信息

• 作为反应物：
  描述：

  (η(5)-EtMe2SiC5H4)(η(5)-C5H5)ZrCl2 、 三溴化硼 以 1,2-二氯乙烷 为溶剂， 生成 (η(5)-BrMe(Et)SiC5H4)(η(5)-C5H5)ZrBr2
  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：

  (η5-cyclopentadienyl)trichlorozirconium dimethoxyethane 、 以 甲苯 为溶剂， 以76%的产率得到(η(5)-EtMe2SiC5H4)(η(5)-C5H5)ZrCl2
  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