[TaCl3(η2-(3-hexyne))(pyridine)2] | 401846-35-3

• 英文名称: [TaCl3(η2-(3-hexyne))(pyridine)2]
• 英文别名: [TaCl3(η2-EtCCEt)(pyridine)2]
• CAS: 401846-35-3
• 化学式: C₁₆H₂₀Cl₃N₂Ta
• 分子量: 527.655
• InChiKey: IPEKVSYEPPMBMX-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

• 作为反应物：
  描述：

  [TaCl3(η2-(3-hexyne))(pyridine)2] 、 丙酮 以 氘代甲苯 为溶剂， 生成
  参考文献：
  名称：

  Preparation, Structural Characterization, and Reactions of Tantalum-Alkyne Complexes TaCl₃(R¹C⋮CR²)L₂ (L₂ = DME, Bipy, and TMEDA; L = Py)

  摘要：

  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.

  DOI：

  10.1021/om020510x
• 作为产物：
  描述：

  吡啶 、 (η²-EtCCEt)TaCl₃(1,2-dimethoxyethane) 以 甲苯 为溶剂， 以42%的产率得到[TaCl3(η2-(3-hexyne))(pyridine)2]
  参考文献：
  名称：

  Preparation, Structural Characterization, and Reactions of Tantalum-Alkyne Complexes TaCl₃(R¹C⋮CR²)L₂ (L₂ = DME, Bipy, and TMEDA; L = Py)

  摘要：

  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.

  DOI：

  10.1021/om020510x
• 作为试剂：
  描述：

  1-己炔 在 [TaCl3(η2-(3-hexyne))(pyridine)2] 作用下， 以 甲苯 为溶剂， 反应 1.5h， 生成 1,3,5-三丁基苯 、 1,2,4-三丁基苯
  参考文献：
  名称：

  Catalytic Performance of Tantalum–η²-Alkyne Complexes [TaCl₃(R¹C≡CR²)L₂] for Alkyne Cyclotrimerization

  摘要：

  结构上表征的钽–η2-炔烃配合物 [TaCl3(η2-EtC≡CEt)L2] (1, L2 = 1,2-二甲氧乙烷 (DME); 2, L = 呋喃) 作为催化剂用于末端炔烃的环三聚反应。催化反应在25°C下进行，仅需几小时，便可获得三取代苯类化合物，而没有形成线性 oligomers。制备了一种新的钽配合物，具有末端炔烃配体 [TaCl3(η2-Me3SiC≡CH)(dme)] (3)，并对其催化性能进行了研究。

  DOI：

  10.1246/bcsj.77.1009