(η5-C5Me5)2TaH(CH2=CH2) | 100701-96-0

• 英文名称: (η5-C5Me5)2TaH(CH2=CH2)
• CAS: 100701-96-0
• 化学式: C₂₂H₃₅Ta
• 分子量: 480.468
• InChiKey: NECQMYYAAOWIHA-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：

  (η5-C5Me5)2TaH(CH2=CH2) 在 氧气 作用下， 以 正戊烷 为溶剂， 生成 (η5-C5Me5)2Ta(η2-O2)CH2CH3
  参考文献：
  名称：

  Dioxygen-derived peroxo-alkyl complexes of permethyltantalocene. Structural characterization of (.eta.5-C5Me5)2Ta(.eta.2-O2)(CH2C6H5) and acid-catalyzed rearrangement to oxo-alkoxide derivatives

  摘要：

  DOI：

  10.1021/ja00232a058
• 作为产物：
  描述：

  Cp₂*TaCl₂ 生成 (η5-C5Me5)2TaH(CH2=CH2)
  参考文献：
  名称：

  烯烃插入铌-和钽-氢化物键的动力学和机制：空间和电子效应之间的竞争研究

  摘要：

  烯烃插入过渡金属-氢化物键的机理已经被研究了一系列的铌茂、全甲基铌茂、钽茂和全甲基钽茂的烯烃氢化物配合物。测量了几个 permethylniobocene 的间位取代苯乙烯配合物的插入率，发现与对位取代类似物的插入率相当，表明电子效应在很大程度上是诱导性的。母体苯乙烯复合物的 X 射线晶体结构测定 (P/sub bca/; a = 14.626 (3) A, b = 18.134 (4) A, c = 18.147 (4) A;..cap alpha.., ..beta.., ..gamma.. = 90/sup 0/) 为这一观察结果提供了一个解释：苯环因与烯烃 ..pi.. 系统共振而弯曲 32/sup 0/。对整个乙烯化合物系列（其中空间效应最小）的速率的比较表明，在该系列中存在显着的电子效应（k/sub Nb/ > k/sub Cp/；Cp = (eta/sup 5 /-C/sub

  DOI：

  10.1021/ja00218a023

文献信息

• The ansa-effect in permethyltantalocene chemistry: a [Me2Si] ansa bridge promotes olefin-insertion and reductive-elimination reactions for [Me2Si(C5Me4)2]Ta(η2-C2H4)H and [Me2Si(C5Me4)2]TaH3
  作者：Jun Ho Shin、Gerard Parkin

  DOI：10.1039/a900895k

  日期：——

  The ansa-effect, as it applies to tantalocene chemistry, has been investigated by a comparison of the chemistry of [Me2Si(C5Me4)2]TaH3 and [Me2Si(C5Me4)2]Ta(η2-C2H4)H with their permethyltantalocene counterparts; these studies demonstrate that incorporation of the [Me2Si] ansa bridge substantially enhances the rates of both reductive elimination of H2 and ethylene-insertion into a Ta–H bond.

  通过比较 [Me2Si(C5Me4)2]TaH3 和 [Me2Si(C5Me4)2]Ta(β2-C2H4)H 与其全甲基钽茂的化学性质，研究了适用于钽茂化学的 ansa 效应同行；这些研究表明，[Me2Si] ansa 桥的掺入大大提高了 H2 的还原消除率和乙烯插入 Ta–H 键的速率。
• Mechanistic Studies on the Addition of Dihydrogen to Tantalocene Complexes
  作者：Dawn C. Bregel、Susan M. Oldham、Richard Eisenberg

  DOI：10.1021/ja027005b

  日期：2002.11.1

  the two hydride ligands. The results thus support a mechanistic pathway of H(2) addition to an unsaturated Ta(III) intermediate, [Cp(2)Ta(CH(3))], rather than addition directly across the Ta=C bond. In a same sample comparison, the rates of initial H(2) addition and subsequent C-H reductive elimination for both Cp(2)Ta(CH(2))(H) and Cp(2)Ta(C(6)H(4))(H) were examined. The methylene complex exhibits

  使用副氢诱导极化 (PHIP)、(13)C 标记以及与相关复合物 Cp(2)Ta(CH) 的比较，研究了向 Cp(2)Ta(CH(2))(H) 添加二氢的机制(2))(CH(3))。对位富集氢与 Cp(2)Ta(CH(2))(H) 的反应导致 Cp(2)Ta(CH(3))(H)(2) 和 Cp(2) 的极化共振TaH(3)，即使在最早的反应时间。使用标记化合物 Cp(2)Ta((13)CH(2))(H) 表明 Cp(2)Ta(CH(3))(H)(2) 的极化共振对应于两个氢化物配体。因此，结果支持 H(2) 添加到不饱和 Ta(III) 中间体 [Cp(2)Ta(CH(3))] 的机械途径，而不是直接通过 Ta=C 键添加。在同一个样本比较中，Cp(2)Ta(CH(2))(H) 和 Cp(2)Ta(C(6)H(4))(H) 的初始 H(2) 添加率和随后的 CH 还原消除率分别为审查。亚甲
• Synthesis and characterization of (η5-C5Me5) 2TaCl(THF), a useful synthetic precursor for the preparation of oxo, imido and methylidene derivatives of permethyltantalocene
  作者：David M. Antonelli、William P. Schaefer、Gerard Parkin、John E. Bercaw

  DOI：10.1016/0022-328x(93)83360-8

  日期：1993.12

  The synthesis and characterization of Cp*Ta-2(=O)Cl (Cp*=(eta(5)-C(5)Me(5))), Cp*Ta-2(=NPh)Cl, Cp*Ta-2(=O)H, Cp*Ta-2(=NR)H (R=Ph, CMe(3)), Cp*Ta-2(=CH2)H, Cp*Ta-2(=CH2)Cl, Cp*Ta-2(H2C=CH2)H, and the unusual cyclometallated product Cp*(eta(6)-C(5)Me(4)CH(2))TaH2 from Cp*2TaCl(THF) (THF = tetrahydrofuran) is described. Cp*2TaCl(THF) is prepared by the Na/Hg reduction of Cp*2TaCl2 in THF and used in situ. These synthetic routes are more convenient than those previously described and in most cases give much higher yields and purer products. All attempts to isolate Cp*2TaCl(THF) as a pure crystalline solid have led instead to less reactive [Cp*2TaCl](n), whose structure is uncertain. Although Cp*2TaCl(THF) is only moderately stable in THF at room temperature, it has been characterized in solution by H-1 NMR spectroscopy. Both [Cp*2TaCl](n) and Cp*2TaCl(THF) react with CO to afford Cp*2TaCl(CO), An X-ray crystal structure determination for Cp*Ta-2(=NPh)Cl (triclinic space group P (1) over bar (number 2) with Z = 2; a = 8.627(2); b = 9.538(5), c = 16.890(5) Angstrom alpha= 74.81(3)degrees, beta = 87.12(2)degrees, gamma = 63.79(3)degrees, with V = 1200.0(8) Angstrom(3)) reveals a linear Ta-N-C group, as had been found previously for the closely related complex Cp*Ta-2(=NPh)H.
• Bent-sandwich derivatives of tantalum bearing one or two pentamethylcyclopentadienyl ligands
  作者：Vernon C. Gibson、John E. Bercaw、William J. Bruton、Robert D. Sanner

  DOI：10.1021/om00136a023

  日期：1986.5.1
• McDade, Christine; Gibson, Vernon C.; Santarsiero, Bernard D., Organometallics, 1988, vol. 7, # 1, p. 1 - 7
  作者：McDade, Christine、Gibson, Vernon C.、Santarsiero, Bernard D.、Bercaw, John E.

  DOI：——

  日期：——