fac-[TaCl(NMe2)3(i-PrNC(H)NPr-i)] | 1344017-82-8

• 英文名称: fac-[TaCl(NMe2)3(i-PrNC(H)NPr-i)]
• CAS: 1344017-82-8
• 化学式: C₁₃H₃₃ClN₅Ta
• 分子量: 475.839
• InChiKey: PKKBGOLSYWZDDP-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：

  fac-[TaCl(NMe2)3(i-PrNC(H)NPr-i)] 、 3-Butenylmagnesium bromide 以 四氢呋喃 、 正戊烷 为溶剂， 以67%的产率得到fac-[TaCl(NMe2)3(η1-3-butenyl)(i-PrNC(H)NPr-i)]
  参考文献：
  名称：

  Allyl Ligand Reactivity in Tantalum(V) Compounds: Experimental and Computational Evidence for Allyl Transfer to the Formamidinate Ligand in fac-Ta(NMe₂)₃(η¹-allyl)[ⁱPrNC(H)NⁱPr] via a Metallo-Claisen Rearrangement

  摘要：

  Treatment of TaCl(NMe2)(4) (1) with allylMgCl furnishes the allyl-substituted compound Ta(NMe2)(4)(eta(1)-allyl) (2) in moderate yield. The X-ray structure of 2 reveals a trigonal-bipyramidal geometry at the tantalum center with an equatorially situated eta(1)-allyl moiety. VT H-1 NMR measurements confirm that the molecule is fluxional in solution over the temperature range 298-193 K, and DFT calculations indicate that the time-averaged environment exhibited 1:1 the allyl moiety in fluid solution derives from a rapid eta(1)-to-eta(3) equilibration, with Ta(NMe2)(4)(eta(3)-allyl) serving as the transition state for this process. 1 reacts rapidly with the formarnidine (PrNC)-Pr-i-(H)(NHPr)-Pr-i to yield fac-TaCl(NMe2)(3)[(PrNC)-Pr-i(H)(NPr)-Pr-i] (5) and Me2NH, and the tantalum product has been characterized by NMR spectroscopy and X-ray diffraction analysis. The five-coordinate compound Ta(NMe2)(3)[(PrNCH)-Pr-i(allyl)(NPr)-Pr-i] (7), whose origin is traced to the putative octahedral species fac-Ta(NMe2)(3)(eta(1)-allyl) [(PrNC)-Pr-i(H)(NPr)-Pr-i] (6), has been obtained from the reaction of 2 with (PrNC)-Pr-i(H)(NHPr)-Pr-i; 7 may also be prepared from the reaction of 5 with allylMgCl. The rearrangement of the allyl moiety in fac-Ta(NMe2)(3)(eta(1)-allyl)[(PrNC)-Pr-i(H)(NPr)-Pr-i] to the formamidinate carbon atom in 7 has been investigated by DFT calculations. Here the DFT calculations have provided crucial insight into the reaction mechanism and the composition of those transient species that do not lend themselves to direct spectroscopic observation. The computed barrier for this metallo-Claisen rearrangement is sensitive to the nature of the density functional employed, and the barrier computed using the meta-GGA TPSS functional provides the best agreement with the experimental conditions. The related alkenyl derivatives Ta(NMe2)(4)(eta(1)-3-butenyl) (3) and Ta(NMe2)(3)(eta(1)-3-butenyl)[(PrNC)-Pr-i(H)(NPr)-Pr-i] (8) have been synthesized, and their reactivity is contrasted with the corresponding allyl-substituted analogues.

  DOI：

  10.1021/om200683q
• 作为产物：
  描述：

  tetrakis(dimethylamino)tantalum chloride 、 N,N'-Diisopropylformamidin 以 正戊烷 为溶剂， 以75%的产率得到fac-[TaCl(NMe2)3(i-PrNC(H)NPr-i)]
  参考文献：
  名称：

  Allyl Ligand Reactivity in Tantalum(V) Compounds: Experimental and Computational Evidence for Allyl Transfer to the Formamidinate Ligand in fac-Ta(NMe₂)₃(η¹-allyl)[ⁱPrNC(H)NⁱPr] via a Metallo-Claisen Rearrangement

  摘要：

  Treatment of TaCl(NMe2)(4) (1) with allylMgCl furnishes the allyl-substituted compound Ta(NMe2)(4)(eta(1)-allyl) (2) in moderate yield. The X-ray structure of 2 reveals a trigonal-bipyramidal geometry at the tantalum center with an equatorially situated eta(1)-allyl moiety. VT H-1 NMR measurements confirm that the molecule is fluxional in solution over the temperature range 298-193 K, and DFT calculations indicate that the time-averaged environment exhibited 1:1 the allyl moiety in fluid solution derives from a rapid eta(1)-to-eta(3) equilibration, with Ta(NMe2)(4)(eta(3)-allyl) serving as the transition state for this process. 1 reacts rapidly with the formarnidine (PrNC)-Pr-i-(H)(NHPr)-Pr-i to yield fac-TaCl(NMe2)(3)[(PrNC)-Pr-i(H)(NPr)-Pr-i] (5) and Me2NH, and the tantalum product has been characterized by NMR spectroscopy and X-ray diffraction analysis. The five-coordinate compound Ta(NMe2)(3)[(PrNCH)-Pr-i(allyl)(NPr)-Pr-i] (7), whose origin is traced to the putative octahedral species fac-Ta(NMe2)(3)(eta(1)-allyl) [(PrNC)-Pr-i(H)(NPr)-Pr-i] (6), has been obtained from the reaction of 2 with (PrNC)-Pr-i(H)(NHPr)-Pr-i; 7 may also be prepared from the reaction of 5 with allylMgCl. The rearrangement of the allyl moiety in fac-Ta(NMe2)(3)(eta(1)-allyl)[(PrNC)-Pr-i(H)(NPr)-Pr-i] to the formamidinate carbon atom in 7 has been investigated by DFT calculations. Here the DFT calculations have provided crucial insight into the reaction mechanism and the composition of those transient species that do not lend themselves to direct spectroscopic observation. The computed barrier for this metallo-Claisen rearrangement is sensitive to the nature of the density functional employed, and the barrier computed using the meta-GGA TPSS functional provides the best agreement with the experimental conditions. The related alkenyl derivatives Ta(NMe2)(4)(eta(1)-3-butenyl) (3) and Ta(NMe2)(3)(eta(1)-3-butenyl)[(PrNC)-Pr-i(H)(NPr)-Pr-i] (8) have been synthesized, and their reactivity is contrasted with the corresponding allyl-substituted analogues.

  DOI：

  10.1021/om200683q

文献信息

• New azido-substituted tantalum compounds: syntheses and DFT examination of nitrogen-rich mono-, di-, and trinuclear tantalum(v) compounds
  作者：Shih-Huang Huang、Vladimir N. Nesterov、Michael G. Richmond

  DOI：10.1039/c3dt53101e

  日期：——

  formamidine iPrNC(H)NHiPr to furnish fac-Ta(NMe2)3(η1-N3)[iPrNC(H)NiPr] (2) and Me2NH; compound 2 has been characterized by IR and 1H NMR spectroscopy and X-ray diffraction analysis. Treatment of 1 with p-toluidine affords the trinuclear compound Ta3(NMe2)5(μ-NMe2)(μ-NC6H4Me-4)2(NC6H4Me-4)(μ-N3)2(η1-N3) (3). Compound 3 contains three non-bonded tantalum atoms that are ligated by edge-bridging imido, amido

  描述了含有辅助叠氮基配体的新钽化合物的合成。由TACl（NMe 2）4与NaN 3在THF中的反应以高收率合成了具有TA（NMe 2）4（N 3）组成的钽化合物。固态结构显示基于TA构成的二聚体结构2（NME 2）8（μ-N 3）2（1），其中8元dimeTAllocyclic环具有像椅子的构象具有桥接叠氮配体结合的两个TA （NMe 2）4部分。溶液分子量测量和电子结构计算预测1在室温下以单体形式存在。1种发生反应与甲脒我PRNC（H）NH我镨到配料FAC -TA（NME 2）3（η 1 -N 3）[我PRNC（H）N我镨]（2）和Me 2 NH; 通过IR和1 H NMR光谱法和X射线衍射分析对化合物2进行了表征。用p处理1甲苯胺，得到三核化合物的TA 3（NME 2）5（μ-NME 2）（μ-NC 6 H ^ 4 ME-4）2（NC 6 H ^ 4 ME-4）（μ-N 3）2（η 1