(quinoline)Ta(O-2,6-C6H3i-Pr2)3Cl2(OEt2) | 111618-74-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (quinoline)Ta(O-2,6-C6H3i-Pr2)3Cl2(OEt2)
• CAS: 111618-74-7
• 化学式: C₄₀H₆₁Cl₂O₄Ta
• 分子量: 857.776
• InChiKey: LGBBZCZAAAADLE-UHFFFAOYSA-I

计算性质

• 辛醇/水分配系数(LogP)：
  13.75
• 重原子数：
  47.0
• 可旋转键数：
  14.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (quinoline)Ta(O-2,6-C6H3i-Pr2)3Cl2(OEt2) 在 NaHg 作用下， 以 乙醚 、 正戊烷 为溶剂， 生成 (η2-(N,C)-quinoline)Ta(O-2,6-C6H3i-Pr2)3
  参考文献：
  名称：

  喹啉键合模式与氧化态负载的钽配合物中氧化态的关系：加氢脱氮催化模型

  摘要：

  摘要杂环配合物[η1（N）-QUIN] Ta（OAr）3 Cl 2（1）和[η1（N）-6MQ] Ta（OAr）3 Cl 2（2）（其中Ar = 2,6 -二异丙基苯基，QUIN ＝喹啉，和6MQ ＝ 6-甲基喹啉）由Ta（OAr）3 Cl 2（OEt 2）和QUIN或6MQ在戊烷中制备。由Ta（OAr）2 Cl 3（OEt 2）类似地制备[η1（N）-6MQ] Ta（OAr）2 Cl 3（4）。通过这些化合物的快速双电子还原，实现了η1（N）→η2（N，C）键重排，并且形成了热敏感的d 2物种[η2（N，C）-QUIN] Ta（ OAr）3（5），[η2（N，C）-6MQ] Ta（OAr）3（6）和[η2（N，C）-6MQ] Ta（OAr）2 Cl（OEt 2）（ 9）可以隔离。或者，可以由（η6 -C 6 Me 6）Ta（OAr）2 Cl和6MQ以更高的产率制备[η2（N，C）-6MQ]

  DOI：

  10.1016/0277-5387(95)85013-9
• 作为产物：
  描述：

  lithium 2,6-diisopropylphenolate 、 五氯化钽 在 diethyl ether 作用下， 以 乙醚 为溶剂， 以87%的产率得到(quinoline)Ta(O-2,6-C6H3i-Pr2)3Cl2(OEt2)
  参考文献：
  名称：

  钽（V）的立体拥塞三苯酚配合物。[TaCl 2（2,6-二叔丁氧基苯酚）3 ]和[Ta 2 Cl（μ-Cl）2（2,6-二异丙氧基苯酚）5（μ-O）]的x射线晶体结构

  摘要：

  TaCl 5与苯中的两个当量的2,6-二叔丁基苯氧基锂反应，以70％的收率和三当量的[TaCl 3（2,6-二叔丁基苯氧基）2 ]（1）生成。在乙醚中的苯氧基锂形成[TaCl 2（2,6-二叔丁基苯氧基）3 ]（2），也可以通过（1）与一当量的苯氧基锂反应制备。三当量的2,6-二异丙基苯氧基锂与TaCl 5反应，得到[TaCl 2（二乙醚）（2,6-二异丙基苯氧基）3 ]（4），其尝试在空气存在下重结晶，得到[Ta 2 Cl（μ-Cl）2（2,6-二异丙基苯氧基）5（μ-O）]（5）。配合物（1），（2）和（4）通过元素分析，IR，1 H和13 C NMR谱表征。在（酚盐配位体的配位2）是伴随着苯环的低磁场位移本位，邻和对位分别碳的9.6，3.6和3.1 ppm的共振，与游离的配体进行比较。对于复杂（4）相对位移为5.9、6.1和2.9 ppm。（2）和（5）的结构已经通过单晶X射线衍射法确定。的（晶体2）是单斜晶系，空间群P

  DOI：

  10.1016/s0277-5387(00)86548-1

文献信息

• Homogeneous models for hydrodenitrogenation catalysis
  作者：Keith J. Weller、Peter A. Fox、Steven D. Gray、David E. Wigley

  DOI：10.1016/s0277-5387(96)00610-9

  日期：1997.1

  Hydrodenitrogenation (HDN) catalysis is the process of removing nitrogen from petroleum feedstocks in the form of NH3 to provide more processable and environmentally compatible liquid fuels. In practice, HDN is carried out simultaneously with other catalytic hydrotreating reactions such as hydrodesulfurization (HDS), yet HDN is significantly less well-studied than HDS. This contribution provides an overview of the heterogeneous HDN process, then outlines various homogeneous models for hydrodenitrogenation catalysis including binding modes of HDN substrates, catalytic hydrogenation processes and recent C--N bond cleavage reactions of nitrogen heterocycles. Emphasis is placed on aryloxide and alkoxide complexes of the early metals that afford some of the best homogeneous models for hydrodenitrogenation catalysis to date. (C) 1997 Elsevier Science Ltd.
• Cross-coupling reactions of d2 tantalum alkyne complexes: selective 1,3-diene syntheses and their relevance to alkyne cyclization chemistry
  作者：Jamie R. Strickler、Pamela A. Wexler、David E. Wigley

  DOI：10.1021/om00047a038

  日期：1991.1

  Ta(DIPP)3Cl2(OEt2) (DIPP = 2,6-diisopropylphenoxide) can be reduced by two electrons in the presence of the bulky alkynes PhC = CPh and Me3SiC = CMe to provide the pale yellow adducts (DIPP)3Ta-(PhC = CPh) (1) and (DIPP)3Ta(Me3SiC = CMe) (2). The reduction of Ta(DIPP)3Cl2(OEt2) in the presence of smaller internal alkynes (viz. EtC = CEt) or the terminal alkynes Me3SiC = CH or Me3CC = CH affords the metallacyclopentadienes (DIPP)3Ta-activated-(CEt = CEtCet = CEt) (3) or (DIPP)3Ta-activated-(CR = CHCR = CH) (4, R = SiMe3; 5, R = CMe3) directly. The molecular structure of the PhC = CPh adduct 1 is approximately tetrahedral (L-Ta-L angles average 109.4-degrees) and features very short Ta-C(alkyne) distances (2.070 (3) and 2.076 (3) angstrom, respectively) and an elongated "C = C" bond (1.346 (5) angstrom), which indicate a strongly bound and substantially reduced alkyne ligand. The molecular structure of metallacycle 3 reveals a trigonal bipyramidal geometry (L(ax)-Ta-L(ax) = 164.9 (3)-degrees) with the metallacyclic alpha carbons occupying one axial and one equatorial site. The alkyne complex (DIPP)3Ta(PhC = CPh) (1) reacts with MeC = CMe, EtC = CEt, Me3CC = CH, Me3SiC = CH, or PhC = CH to afford high yields of the metallacyclization products (DIPP)3Ta-activated-a(CPh = CPhCMe = CMe) (6), (DIPP)3Ta(CPh = CPhCEt = CEt) (7), (DIPP)3 Ta-activated (CPh = CPhCH = CCMe3) (8), (DIPP)3Ta-activated-(CPh = CPh CPhCH=?? = CSiMe3) (9), and (DIPP)3 Ta-acitvated-(CPh = CPhCH = CPh) (10), respectively, while 1,7-octadiyne HC = C(CH2)4C = CH reacts with 2 equiv of (DIPP)3Ta(PhC = CPh) to provide the unusual bimetallic complex (DIPP)3T-activated-a(CPh = CPhCH = C(CH2)4- C = CHCPh = PhC)Ta(DIPP)3 (11). The alkyne adduct (DIPP)3 Ta(Me3SiC = CMe) (2) also engages in metallacyclization chemistry as it reacts with MeC = CMe to afford (DIPP)3T-activated-a(CMe = CSiMe3CMe = CMe) (12), with PhC = CH to provide (DIPP)3T-activated-a(CSiMe3 = CMeCPh = CH) (13), and with Me3CC = CH to afford (DIPP)3T-activated-a(CCMe3 = CHCSiMe3 = CMe) (14). All of the metallacyclopentadiene complexes can be hydrolyzedwith H2O/ acetone solutions to afford the corresponding 1,3-dienes in essentially quantitative yields. However, iodination of metallacycles 6, 7, and 13 does not yield the expected 1,4-diiodo-1,3-dienes but rather the ring-opened monoiodinated butadienyl compounds (DIPP)3(I)TaCPh = CPhCMe = CMe(I) (15), (DIPP)3(I)TaCPh = CPhCEt = CEt(I) (16), and (DIPP)3(I)TaCSiMe3 = CMeCPh = CH(I) (17), respectively. The subsequent hydrolysis of compounds 15-17 provides the corresponding 1-iodo-1,3-dienes.
• Gray, Steven D.; Smith, David F.; Bruck, Michael A., Journal of the American Chemical Society, 1992, vol. 114, # 13, p. 5462 - 5463
  作者：Gray, Steven D.、Smith, David F.、Bruck, Michael A.、Wigley, David E.

  DOI：——

  日期：——
• Strickler; Bruck; Wexler, Organometallics, 1990, vol. 9, # 1, p. 266 - 273
  作者：Strickler、Bruck、Wexler、Wigley

  DOI：——

  日期：——
• Alkyne cyclizations at reduced tantalum centers: synthesis and molecular structure of (.eta.6-C6Me6)Ta(O-2,6-i-Pr2C6H3)2Cl
  作者：M. A. Bruck、A. S. Copenhaver、D. E. Wigley

  DOI：10.1021/ja00255a056

  日期：1987.10