Ta(η(4)-tribenzylidenemethane)Me2Cl | 171508-08-0

• 英文名称: Ta(η(4)-tribenzylidenemethane)Me2Cl
• CAS: 171508-08-0
• 化学式: C₂₄H₂₄ClTa
• 分子量: 528.855
• InChiKey: FBPAONGLCYESKJ-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：

  Ta(η(4)-tribenzylidenemethane)Me2Cl 、 lithium diphenylamide 以 四氢呋喃 为溶剂， 以83%的产率得到
  参考文献：
  名称：

  Binding Preferences of the Tribenzylidenemethane Ligand in High-Oxidation-State Tantalum Complexes

  摘要：

  Reaction of Li-2(TBM)(TMEDA)(2) (TBM = tribenzylidenemethane) with TaMe3Cl2 gives (TBM)-TaMe3 (1) in 44% yield. Structural characterization of the (tert-Bu-TBM)TaMe3 derivative 2 shows an eclipsed orientation of the TaMe3 tripod relative to the inner core of the TBM ligand. Treatment of(TBM)TaMe3 with ZnCl2 cleanly replaces one methyl ligand for chloride to give (TBM)TaMe2Cl (3) which is a versatile precursor to (TBM)Ta-based complexes. Addition of LiNPh2 to 3 gives (TBM)TaMe2(NPh2) (4). Structural characterization reveals that both 3 and 4 have eclipsed frameworks. Metallocene-mimics are accessible by reacting LiCp (Cp = C5H5), LiCp* (Cp* = C5Me5), LiCp' (Cp' = C5H4Me), or LiFlu (Flu = fluorenyl) with 3 to give Cp(TBM)TaMe2 (5), Cp*(TBM)TaMe2 (6), Cp'(TBM)TaMe2 (7), and Flu(TBM)TaMe2 (8), respectively. The solid-state structures of 5, 7, and 8 display gross molecular geometries similar to those of group 3 metallocenes. Complex 3 reacts with tris(pyrazolylborate) or bis(pyrazolylborate) salts. Thus, [HB (pz)(3)](TBM)TaMe2 (9), [HB(3,5-Me-2-1-pz)(3)](TBM)TaMe2 (10), and [H2B(pz)(2)] (TBM)TaMe2 (11) are obtained from Na[HB(pz)(3)], K[HB(3,5-Me-2-1-pz)(3)], and K[H2B(pz)(2)], respectively. Structural characterization of 9, 10, and 11 shows that TBM can adopt a continuum of bonding modes, from eta(4) to eta(2), depending on the steric hindrance around the metal center. The TMM ligand participates in hydrogenation and insertion reactions, indicating that TMM is a weak ancillary ligand. Combining 6, 7, or 8 with MAO results in short-lived ethylene polymerization catalysts. Finally, an electronic description of the model complex (TMM)TaMe3 is developed to account for the eclipsed molecular structures of 1-4. A comparison against the orbital description of staggered (TMM)Fe(CO)(3) is also made.

  DOI：

  10.1021/ja981640t
• 作为产物：
  描述：

  以 二氯甲烷 为溶剂， 以99%的产率得到Ta(η(4)-tribenzylidenemethane)Me2Cl
  参考文献：
  名称：

  Neutral Group V Bent Metallocene Analogs Containing the Tribenzylidenemethane Dianion

  摘要：

  DOI：

  10.1021/ja00145a044

文献信息

• Synthesis of two tantalum complexes bearing cyclopentadienyl analogs
  作者：Caroline K. Sperry、George Rodriguez、Guillermo C. Bazan

  DOI：10.1016/s0022-328x(97)00054-5

  日期：1997.12

  Reaction of Li[C5H5B-NMe2] with (TBM)TaMe2Cl (TBM = tribenzylidenemethane) gives (TBM)[C5H5B-NMe2]TaMe2 (1). A single crystal diffraction study revealed a metallocene-like environment with the metal binding more strongly to the boratabenzene ring carbons furthest from the boron atom. (2) (Cp∗ = C5Me5) is obtained from the reaction of Cp∗[C4H4B-N(CHMe2)2]TaCl2 and (C4H6Mg)(THF)2. The diene fragment

  Li [C 5 H 5 B-NMe 2 ]与（TBM）TaMe 2 Cl（TBM ＝三亚苄基甲烷）反应，得到（TBM）[C 5 H 5 B-NMe 2 ] TaMe 2（1）。单晶衍射研究表明，类似茂金属的环境中，金属与硼原子距离最远的硼烷基苯环碳更牢固地结合。（2）（Cp ∗ = C 5 Me 5）由Cp ∗ [C 4 H 4 B-N（CHMe 2）2 ] TaCl反应制得2和（C 4 H 6 Mg）（THF）2。二烯片段以反式构型结合。如果考虑所有共振贡献，则钽在2中的氧化态可被认为是I，III或V。