cp2ZrMe(OMes) | 185542-73-8

• 英文名称: cp2ZrMe(OMes)
• 英文别名: bis(η(5)-cyclopentadienyl)methylzirconium 2,4,6-trimethylphenoxide；cp₂ZrMe(OMes)；Cp2Zr(Me)OMes
• CAS: 185542-73-8
• 化学式: C₂₀H₂₄OZr
• 分子量: 371.634
• InChiKey: DNFSZQWPVRRMHD-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

• 作为反应物：
  描述：

  cp2ZrMe(OMes) 、 triphenylcarbenium tetra(pentafluorophenyl)borate 以 氟苯 为溶剂， 生成 [Cp₂ZrOMes][B(C₆F₅)₄]
  参考文献：
  名称：

  沮丧的路易斯对机理对锆催化的亚胺加氢反应

  摘要：

  Zirconium-based frustrated Lewis pairs (FLPs) are active imine hydrogenation catalysts under mild conditions. Complexes of the type [Cp(2)(R)ZrOMes][B(C6F3)(4)]-utilize the imine substrate itself as the Lewis base component of the FLP,. Catalyst performance is a function of ligand structure; in general more bulky, more electron rich cyclopentadienyl derivatives give the best results, However, Cp* derivatives are not catalytically active, being stable after initial heterolytic cleavage Of H-2; this allows experimental verification of the competence of the zirconocene-imine pair in FLP-type heterolytic H-2 cleavage. Enamines and protected nitriles are also hydrogenated if an additional internal phosphine base is used.

  DOI：

  10.1021/acs.organomet.6b00027
• 作为产物：
  描述：

  [Zr((SiMe2)(η(5)-C5H4)2)(CH3)2] 、 2,4,6-三甲酚 以 正己烷 为溶剂， 反应 1.0h， 以78%的产率得到cp2ZrMe(OMes)
  参考文献：
  名称：

  沮丧的路易斯对机理对锆催化的亚胺加氢反应

  摘要：

  Zirconium-based frustrated Lewis pairs (FLPs) are active imine hydrogenation catalysts under mild conditions. Complexes of the type [Cp(2)(R)ZrOMes][B(C6F3)(4)]-utilize the imine substrate itself as the Lewis base component of the FLP,. Catalyst performance is a function of ligand structure; in general more bulky, more electron rich cyclopentadienyl derivatives give the best results, However, Cp* derivatives are not catalytically active, being stable after initial heterolytic cleavage Of H-2; this allows experimental verification of the competence of the zirconocene-imine pair in FLP-type heterolytic H-2 cleavage. Enamines and protected nitriles are also hydrogenated if an additional internal phosphine base is used.

  DOI：

  10.1021/acs.organomet.6b00027

文献信息

• Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs
  作者：Owen J. Metters、Sebastian J. K. Forrest、Hazel A. Sparkes、Ian Manners、Duncan F. Wass

  DOI：10.1021/jacs.5b12536

  日期：2016.2.17

  electronic characteristics at the Lewis acidic and Lewis basic components, with the three-step syntheses of 10 new intermolecular transition metal FLPs being reported. Systematic variation to the phosphine Lewis base is used to unravel steric considerations, with the surprising conclusion that phosphines with relatively small Tolman steric parameters not only give highly reactive FLPs but are often seen to

  我们报告了基于二茂锆芳氧化物和膦部分的分子间过渡金属受挫路易斯对 (FLPs)，它们表现出广泛的小分子活化化学，以前仅保留分子内对。报告了与 D2、CO2、THF 和 PhCCH 的反应。与之前的分子内例子相比，这些系统可以轻松获得路易斯酸性和路易斯碱性成分的各种空间和电子特性，并报告了 10 种新的分子间过渡金属 FLP 的三步合成。膦路易斯碱的系统变异用于解开空间考虑，令人惊讶的结论是，具有相对较小托尔曼空间参数的膦不仅能提供高反应性的 FLP，而且通常被认为对所需产物具有最高的选择性。对这些系统的 DOSY NMR 光谱研究首次揭示了此类过渡金属 FLP 中路易斯酸/路易斯碱相互作用的性质。
• Highly selective monofunctionalization of zirconacyclopentanes and dialkylzirconocene complexes
  作者：Yasushi Nishihara、Koichiro Aoyagi、Ryuichiro Hara、Noriyuki Suzuki、Tamotsu Takahashi

  DOI：10.1016/s0020-1693(96)05301-7

  日期：1996.11

  Selective monofunctionalization was investigated for symmetrical zirconacyclopentanes or symmetrical dialkylzirconocenes. Reaction of zirconacyclopentanes, which were prepared by intermolecular coupling of two alkenes, or intramolecular cyclization of dienes, trienes or tetraenes on zirconium, with PPh(2)Cl or SnR(3)Cl (R = Me, Ph) gave monofunctionalized products in good to high yields with high selectivities. Even in the presence of 2 equiv, of PPh(2)Cl or SnR(3)Cl, only one Zr-carbon bond reacted. Treatment of zirconacycropentanes with methanol yielded monoprotonated complexes. Subsequent addition of halogen such as Br-2 and I-2 to these monoprotonated complexes gave highly selective monohalogenated products. Similar monoprotonation reactions proceeded for dialkylzirconocene or -hafnocene complexes. Reaction of Cp(2)MR(2) (M = Zr or Hf, R = alkyl or aryl) with alcohols afforded alkylalkoxyzirconocene or -hafnocene complexes, Cp(2)MR(OR') (M = Zr or Hf, R' = alkyl or aryl) in high yields with high selectivities. High selectivity of monofunctionalization using PPh(2)Cl, SnR(3)Cl or alcohols can be attributed to the different reactivities between monoalkylzirconocenes which are monofunctionalized products and zirconacyclopentanes or dialkylzirconocenes.