Cp(*)2ZrMe(Np) | 177431-10-6

• 英文名称: Cp(*)2ZrMe(Np)
• 英文别名: Cp(*)2ZrMe(neopentyl)
• CAS: 177431-10-6
• 化学式: C₂₆H₄₄Zr
• 分子量: 447.859
• InChiKey: DMYVWERXDJNBHM-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  Cp(*)2ZrMe(Np) 、 三(五氟苯基)硼烷 以 not given 为溶剂， 生成 Cp(*)2ZrNp(μ-Me)B(C6F5)3
  参考文献：
  名称：

  Mechanistic Study of β-Methyl and β-Hydrogen Elimination in the Zirconocene Compounds Cp‘₂ZrR(μ-CH₃)B(C₆F₅)₃ (Cp‘ = Cp, Cp*; R = CH₂CMe₃, CH₂CHMe₂)

  摘要：

  A kinetics study of beta-methyl elimination reactions of the compounds Cp2ZrNp(mu-Me)B(C6F5)(3) (in various solvents) and Cp*2ZrNp(mu-Me)B(C6F5)(3) (in CD2Cl2) shows that the reactions are accelerated by polar solvents and by steric crowding in the Cp* system, results consistent with previous findings and conclusions that the methyl migrations are accompanied in a concerted process by borate anion departure from the inner coordination sphere of the metal ion. Surprisingly, however, the isobutyl compound CP*Zr-2(i-Bu)(mu-Me)B(C6F5)(3), which is expected to undergo beta-methyl elimination by analogy with an extensive literature on chain transfer processes during propylene polymerization, undergoes very rapid beta-hydrogen elimination only.

  DOI：

  10.1021/om0504710
• 作为产物：
  描述：

  Cp(*)2ZrCl(neopentyl) 、 甲基溴化镁 以 四氢呋喃 、 乙醚 为溶剂， 生成 Cp(*)2ZrMe(Np) 、 Cp(*)2ZrNp2
  参考文献：
  名称：

  Mechanistic Study of β-Methyl and β-Hydrogen Elimination in the Zirconocene Compounds Cp‘₂ZrR(μ-CH₃)B(C₆F₅)₃ (Cp‘ = Cp, Cp*; R = CH₂CMe₃, CH₂CHMe₂)

  摘要：

  A kinetics study of beta-methyl elimination reactions of the compounds Cp2ZrNp(mu-Me)B(C6F5)(3) (in various solvents) and Cp*2ZrNp(mu-Me)B(C6F5)(3) (in CD2Cl2) shows that the reactions are accelerated by polar solvents and by steric crowding in the Cp* system, results consistent with previous findings and conclusions that the methyl migrations are accompanied in a concerted process by borate anion departure from the inner coordination sphere of the metal ion. Surprisingly, however, the isobutyl compound CP*Zr-2(i-Bu)(mu-Me)B(C6F5)(3), which is expected to undergo beta-methyl elimination by analogy with an extensive literature on chain transfer processes during propylene polymerization, undergoes very rapid beta-hydrogen elimination only.

  DOI：

  10.1021/om0504710

文献信息

• Direct Observation of β-Methyl Elimination in Cationic Neopentyl Complexes:  Ligand Effects on the Reversible Elimination of Isobutene
  作者：Andrew D. Horton

  DOI：10.1021/om960089a

  日期：1996.6.11

  beta-Me elimination from cationic neopentyl complexes, [Cp'Zr-2(CH(2)CMe(3))](+), has been demonstrated. The more crowded complex (Cp' = C(5)Me(5)) eliminates isobutene instantaneously at -75 degrees C, whereas the less crowded analogue (Cp' = C5H5) is Stable in solution at 0 degrees C but undergoes reversible beta-Me elimination at 25 degrees C; strong anion or Lewis base coordination suppresses beta-Me elimination, consistent with involvement of a 14-electron species.