zirconocene methyl phenoxide | 256394-31-7

• 英文名称: zirconocene methyl phenoxide
• CAS: 256394-31-7
• 化学式: C₁₇H₁₈OZr
• 分子量: 329.553
• InChiKey: CYCKLKNXUJJUMB-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  bis(cyclopentadienyl)dimethylzirconium(IV) 、 苯酚 以 氘代苯 为溶剂， 生成 zirconocene methyl phenoxide
  参考文献：
  名称：

  用醇盐代替氯化物：Cp 2 Zr（H）OR，寻找Schwartz试剂的替代品

  摘要：

  尝试通过几种合成途径合成锆茂茂氢化醇盐物种Cp 2 Zr（H）OR始终未能产生目标复合物，这些目标复合物似乎易于歧化为Cp 2 ZrH 2和二烷氧化物复合物。Cp 2 ZrH 2与HOR，Me 3 SiOR或Ph 2 CO反应生成相应的双醇盐配合物Cp 2 Zr（OR）2，其中Cp 2 Zr {OC（H）Ph 2 } 2的特征在于X-射线衍射研究。将乙烯基醚插入Cp 2 ZrH 2中得到Cp2 Zr（OR）2和Cp 2 Zr（Et）OR。尝试氢化Cp 2 Zr（Me）OR或Cp 2 Zr（BH 4）OR与NEt 3反应未得到目标复合物。的Cp 2 Zr的（H）OC 6 H ^ 5 1和Cp 2 Zr的（H）OC 6 ˚F 5可以得到，但是，由于自CP过渡形式通过β-H消除2的Zr（吨卜）OR，配位体交换之间的Cp 2 ZrH 2和Cp 2 Zr（OC 6 F 5）2，或在烯烃存在下进行质子

  DOI：

  10.1021/om8008734

文献信息

• Ancillary aryloxide ligands in ethylene polymerization catalyst precursors
  作者：Andrea V Firth、Jeffrey C Stewart、Aaron J Hoskin、Douglas W Stephan

  DOI：10.1016/s0022-328x(99)00422-2

  日期：1999.12

  The compounds CpTiCl2(OC6H3-i-Pr-2) (1), CpTiCl(OC6H3-i-Pr-2)(2) (2), CpTi(R)(OC6H3-i-Pr-2)(2) (R = t-Bu 3, s-Bu 4, n-Bu 5, Me 6) have been prepared and characterized. Compounds 1 or 2 in the presence of 500 equivalents of methylaluminoxane (MAO) act as catalyst precursors for ethylene polymerization. While the catalysts derived from the monocyclopentadienyl complexes are much less active that the metallocenes, there is a clear enhancement in the activity of about 40% as a result of the inclusion of a second aryloxide ligand. Reactions of 1 with AlMe3 revealed stepwise formation of CpTi(Me)Cl(OC6H3-i-Pr-2) 7 and CpTi(Me)(2)(OC6H3-i-Pr-2) 8, while subsequent addition of AlMe3 afforded complete conversion to 8, with formation of the aluminum species [AlMe2(OC6H3-i-Pr-2)](n) 9. In contrast, the catecholate complex CpTi(O2C6H4)Cl 10 reacts with AlMe3 yielding the paramagnetic species [CpTi(O-2(C6H4)). AlClMe2], 11. Incorporation of aryloxide ligands in modified metallocenes was readily accomplished with the preparation of Cp2ZrCl(OC6H3-i-Pr-2) 12, Cp2ZrCl(OC6H5) 13, Cp2ZrMe(OC6H5) 14 and Cp2TiCl(OC6H3-i-Pr-2) 15. In combination with MAO, 12, 14 and 15 effect the polymerization of ethylene with an 11% increase in activity over the parent metallocenedichlorides. The implications of the increased activity are considered. Crystallographic data are reported for 2, 3, 6, 9, 11, 12 and 13. (C) 1999 Elsevier Science S.A. All rights reserved.