[TaCl3(diphenylacetylene)(pyridine)2] | 91581-55-4

• 英文名称: [TaCl3(diphenylacetylene)(pyridine)2]
• 英文别名: [TaCl3(diphenylacetylene)(py)2]
• CAS: 91581-55-4
• 化学式: C₂₄H₂₀Cl₃N₂Ta
• 分子量: 623.743
• InChiKey: RILPGKUPSZHKMA-UHFFFAOYSA-K

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

• 作为产物：
  描述：

  [TaCl3(bis(trimethylsilyl)acetylene)(pyridine)2] 、 二苯基乙炔 以 氘代苯 为溶剂， 生成 [TaCl3(diphenylacetylene)(pyridine)2]
  参考文献：
  名称：

  钽甲硅烷基炔配合物的炔交换反应：机理研究及其在制备具有功能性炔的新型钽配合物中的应用（PhC⋮CR（R = COOMe，CONMe 2））

  摘要：

  钽的硅烷基炔配合物，通式为TaCl 3（R 1 C⋮CR 2）L 2（1，R 1 = R 2 = SiMe 3，L 2 = DME; 2，R 1 = SiMe 3，R 2 = Me， L 2＝ DME；6，R 1＝ R 2＝ SiMe 3，L ＝ py；7，R 1＝ SiMe 3，R 2。= Me，L = py）与内部炔烃反应，通过炔烃交换反应生成相应的炔烃配合物。这些甲硅烷基炔配合物是新制备的，并在结构上进行了表征。动力学测量表明，DME配合物1和2的交换反应速率主要取决于配合物的浓度，反应通过解离途径进行。双（吡啶）配合物6和7的交换反应速率较慢。与DME配合物相反，6的交换反应通过缔合交换途径进行，而7的交换机理是一个关联的途径。在交换过程中，两个吡啶配体强烈地与钽中心配位，并且该中间体被提议为双（炔）配合物。通过甲炔交换反应，由甲硅烷基炔配合物制备具有功能性炔的新型钽配合物（PhC⋮CR（R

  DOI：

  10.1021/om060659z

文献信息

• Preparation, Structural Characterization, and Reactions of Tantalum-Alkyne Complexes TaCl₃(R¹C⋮CR²)L₂ (L₂ = DME, Bipy, and TMEDA; L = Py)
  作者：Toshiyuki Oshiki、Kouji Tanaka、Jun Yamada、Takaya Ishiyama、Yasutaka Kataoka、Kazushi Mashima、Kazuhide Tani、Kazuhiko Takai

  DOI：10.1021/om020510x

  日期：2003.2.1

  Tantalum-alkyne complexes with the general formula TaCl3(R(1)CdropCR(2))(dme) (1a, R-1 = R-2 = Et; 1b, R-1 = R-2 = n-C5H11; 1c, R-1 = Ph, R-2 = Me; 1d, R-1 = R-2 = Ph; DME = 1,2-dimethoxyethane) were synthesized by treatment of the corresponding alkynes with a low-valent tantalum derived by reduction of tantalum pentachloride with zinc powder in a mixed solvent of toluene and DME. The DME ligand can be replaced by 2 equiv of pyridine to afford the corresponding dipyridine complexes TaCl3(R(1)CdropCR(2))(py)(2) (2a, R-1 = R-2 = Et; 2b, R-1 = R-2 = n-C5H11; 2c, R-1 = Ph, R-2 = Me; 2d, R-1 = R-2 = Ph). Additionally, the reaction of 1a with the bidentate nitrogen ligands bipyridine and N,N,N',N'-tetramethyethylenediamine (= TMEDA) gave TaCl3(EtCdropCEt)(bipy) (3) and TaCl3(EtCdropCEt)(tmeda) (4), respectively. The eta(2)- and 4e-coordination mode of an alkyne with a large contribution of a metalacyclopropene canonical structure was revealed by spectroscopic methods (NMR and IR) and crystallographic analyses of 1a, 1c, 2a, and 4. The reactivies of the tantalum-3-hexyne complexes la, 2a, 3, and 4 toward 3-phenylpropanal were investigated. Only the pyridine complex 2a reacted with a stoichiometric amount of the aldehyde to afford the corresponding allylic alcohol in 77% yield upon hydrolysis. The reaction proceeded via an oxatantalacyclopentene species.