| 84876-11-9

• CAS: 84876-11-9
• 化学式: C₁₆H₂₇Ta
• 分子量: 400.338
• InChiKey: UFLHGQNMMKAJQI-UHFFFAOYSA-N

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：

  、 2, 6-二甲基苄氰 以 苯 为溶剂， 以95%的产率得到N-(2,6-dimethylphenyl)ethanimine;(2,6-dimethylphenyl)-(4-methanidylpent-4-en-2-yl)azanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tantalum(5+)
  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 正己烷 为溶剂， 以50%的产率得到
  参考文献：
  名称：

  产生新的亚胺、亚胺和三亚甲基甲烷配合物的钽的氢转移反应

  摘要：

  已经检查了 Cp*TaMe3C1 (Cp* = qs-CsMeS) 与各种碱金属醇盐、烷基酰胺和烷基试剂的反应。与 LiNMe2 反应生成 Cp*Ta(NMez)Me3，其在 25 OC 下分解为亚胺（或金属氮杂环）络合物 Cp*Ta(CH2NMe)Me2。分解是具有大动力学同位素效应 (kH/kD = 9.7) 的一级单分子过程。单烷基酰胺 (LiNHR) 与 Cp*TaMe3C1 反应形成亚氨基配合物 Cp*Ta(NR)Mez。Cp*TaMe3C1 与二异丙基氨基锂反应形成桥连亚甲基复合物 Cp*Me2Ta(pCH2)(pH)zTaMezCp*。醇盐化合物 Cp*Ta(OR)Me3 (R = Me, CHMe2, CMe3) 非常稳定，仅在 100 OC 以上分解。只有当烷基不含 j3-氢时，烷基配合物才是稳定的。用 (2-甲基烯丙基 1) 溴化镁处理 Cp*TaMe3C1 得到不稳定的钽

  DOI：

  10.1021/ja00347a023