TaCl₃[N(SiMe₃)₂]₂ | 71616-54-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: TaCl₃[N(SiMe₃)₂]₂
• 英文别名: Trichlorbistantal(V)；Trichlorbis(bis(trimethylsilyl)amido)tantal(V)
• CAS: 71616-54-1
• 化学式: C₁₂H₃₆Cl₃N₂Si₄Ta
• 分子量: 608.08
• InChiKey: CKWJZPUCRKRIJM-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  22.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  TaCl₃[N(SiMe₃)₂]₂ 在 sodium amalgam 作用下， 以 正己烷 为溶剂， 以64%的产率得到
  参考文献：
  名称：

  钽（IV）酰胺和酰亚胺卤化物配合物的合成和晶体结构

  摘要：

  据报道，单体钽（IV）酰氨基卤化物和二聚钽（IV）酰氨基卤化物配合物的合成和晶体结构。

  DOI：

  10.1039/c39930000714
• 作为产物：
  描述：

  lithium hexamethyldisilazane 、 五氯化钽 以 正戊烷 为溶剂， 生成 TaCl₃[N(SiMe₃)₂]₂
  参考文献：
  名称：

  The preparation, characterization and crystal and molecular structure of bis-(bis-trimethylsilylamido)-trichlorotantalum(V)

  摘要：

  DOI：

  10.1016/s0020-1693(00)90933-2

文献信息

• Organoimido-complexes of tantalum(<scp>V</scp>). Preparation and X-ray crystal structure of bis[bis(trimethylsilyl)amido]chloro(t-butylimido)-tantalum(<scp>V</scp>) and bis[bis(trimethylsilyl)amido]-di-µ-bromo-dibromobis-(trimethylsilylimido)ditantalum(<scp>V</scp>)
  作者：Donald C. Bradley、Michael B. Hursthouse、K. M. Abdul Malik、Alistair J. Nielson、George B. Chota Vuru

  DOI：10.1039/dt9840001069

  日期：——

  TaNSi 166.1°) where two chlorines were replaced by bromines and one N(SiMe3)2 ligand was cleaved to generate the TaNSiMe3 moiety. The unsymmetrical bromine bridge was readily disrupted by addition of neutral donor ligands which produced the compounds TaBr2(NSiMe3)[N(SiMe3)2](C5H5N) and TaBr2(NSiMe3)[N(SiMe3)2]-(PMe3). Reaction of TaCl3[N(SiMe3)2]2 with NaS2CNMe2 gave the adduct Ta(NSiMe3)(S2CNMe2)3-(CH2Cl2)

  TaCl 3- [N（SiMe 3）2 ] 2与各种试剂的反应获得了一些新颖的钽有机亚胺配合物。因此，添加LiNHBu t得到单体复合物TaCl（NBu t）[N（SiMe 3）2 ] 2（分子几何参数：Ta N 1.763，Ta – N 1.988和2.029，Ta – Cl 2.322Å； Ta NC 165.8°，晶体结构分析得出的结果）对应于两个氯的置换。与Me 3 SiBr反应导致形成中心对称的五配位二聚体[Ta 2（µ-Br）2 Br 2（NSiMe 3）2 N（SiMe 3）2 } 2 ]（通过X射线结构分析得出Ta N 1.761，Ta–N 1.965，Ta–Br 2.502; Ta–µ-Br 2.655和2.713Å; Ta NSi 166.1°），其中两个氯被溴取代，一个N（SiMe 3）2配体被裂解生成Ta NSiMe 3部分。不对称的溴桥很容易通过添加中性供体配体而破坏，该配体产生化合物TaBr
• Synthesis and Structural Characterization of Tantalum(IV) Amido Compounds
  作者：Seigi Suh、David M. Hoffman

  DOI：10.1021/ic960264f

  日期：1996.1.1

  Tantalum(IV) amido complexes have been synthesized from Ta(V) precursors. Ta(N(SiMe(3))(2))(2)Cl(3) reacts with Na/Hg to give Ta(N(SiMe(3))(2))(2)Cl(2), and Ta(NEt(2))(2)Cl(3) reacts with LiNPh(2) and Na/Hg to yield Ta(NPh(2))(2)(NEt(2))(2). Ta(N(SiMe(3))(2))(2)Ph(2) is prepared by reacting Ta(N(SiMe(3))(2))(2)Cl(2) with LiPh. Attempts to prepare other organometallic derivatives failed to yield clean

  钽（IV）酰胺络合物已由Ta（V）前体合成。Ta（N（SiMe（3））（2））（2）Cl（3）与Na / Hg反应生成Ta（N（SiMe（3））（2））（2）Cl（2）和Ta （NEt（2））（2）Cl（3）与LiNPh（2）和Na / Hg反应生成Ta（NPh（2））（2）（NEt（2））（2）。Ta（N（SiMe（3））（2））（2）Ph（2）是通过使Ta（N（SiMe（3））（2））（2）Cl（2）与LiPh反应制备的。尝试制备其他有机金属衍生物的尝试未能产生清洁产品。X射线晶体学研究显示Ta（N（SiMe（3））（2））（2）Cl（2），Ta（N（SiMe（3））（2））（2）Ph（2）和Ta（NPh（2））（2）（NEt（2））（2）具有扭曲的四面体几何形状。
• Bradley, Donald C.; Hursthouse, Michael B.; Howes, Andrew J., Journal of the Chemical Society, Dalton Transactions
  作者：Bradley, Donald C.、Hursthouse, Michael B.、Howes, Andrew J.、Jelfs, Alasdair N. de M.、Runnacles, John D.、Thornton-Pett, Mark

  DOI：——

  日期：——
• Syntheses and Characterization of Tantalum Alkyl Imides and Amide Imides. DFT Studies of Unusual α-SiMe₃ Abstraction by an Amide Ligand
  作者：Seth C. Hunter、Shu-Jian Chen、Carlos A. Steren、Michael G. Richmond、Zi-Ling Xue

  DOI：10.1021/acs.organomet.5b00558

  日期：2015.12.28

  Reaction of TaCl2(=NSiMe3) [N(SiMe3)(2)] (1) with alkylating reagents form the alkyl amide imide complexes TaR2(=NSiMe3) [N(SiMe3)(2)] (R = Me (2), CH2Ph (3)) and mixed amide imide compounds Ta(NR'(2))(2)(=NSiMe3)-[N(SiMe3)(2)] (R' = Me (4), Et (5)). The reaction of 2 and 0.5 equiv of O-2 leads to preferential oxygen insertion into one Ta-Me bond, yielding the alkoxy-bridged alkyl dimer Ta-2(mu-OMe)(2)Me-2(=NSiMe3)(2)[N(SiMe3)(2)](2) (6) as cis and trans isomers. Crystallization of the cis-6 and trans-6 mixture gave only crystals of trans-6. When the crystals of trans-6 were dissolved in benzene-d(6), conversion of trans-6 to cis-6 occurred until the trans-6 reversible arrow cis-6 equilibrium was reached with K-eq = 0.79(0.02) at 25.0(0.1) degrees C. Kinetic studies of the exchange gave the rate constants k = 0.018(0.002) min(-1) for the trans-6 -> cis-6 conversion and k' = 0.022(0.002) min(-1) for the reverse cis-6 trans-6 conversion at 25.0(0.1) degrees C. Complex 6 reacts with additional 02, forming the dialkoxy dimer Ta-2(mu-OMe)(2)(OMe)(2)(=NSiMe3)(2)[N(SiMe3)(2)](2) (7) as cis and trans isomers. Solid-state structures of 3 and trans-6 have been determined by X-ray diffraction analyses. The mixed amide imide compounds Ta(NR'(2))(2)(=NSiMe3) [N(SiMe3)(2)] (R' = Me (4), Et (5)) have also been prepared by salt metathesis reactions employing TaCl3[N(SiMe3)(2)](2) (8). The pathway from 8 to 4 and 5 eliminates Me3Si-NR'(2) (R' = Me, Et), converting the amide N(SiMe3)(2) ligand to the imide =NSiMe3 ligand. Such intramolecular imidation is rare. The mechanism of this process has been computationally probed, and a-elimination involving the mixed amide species TaCl2(NMe2)[N(SiMe3)(2)](2) (9) is discussed. Diffusion-ordered spectroscopy (DOSY) studies of 1-6 and 8 show that only the alkoxy-bridged cis-6 and trans-6 are dimers in benzene-d(6) solution at 25 degrees C.