bis([1,1':3',1''-terphenyl]-2'-yloxy)tantalum(V) chloride | 116642-99-0

• 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: bis([1,1':3',1''-terphenyl]-2'-yloxy)tantalum(V) chloride
• 英文别名: Ta(OC6H3Ph2-2,6)2Cl3；Ta(2,6-diphenylphenoxide)2Cl3
• CAS: 116642-99-0
• 化学式: C₃₆H₂₆Cl₃O₂Ta
• 分子量: 777.908
• InChiKey: BGNIVICTGHFTTK-UHFFFAOYSA-I

计算性质

• 辛醇/水分配系数(LogP)：
  11.79
• 重原子数：
  42.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  bis([1,1':3',1''-terphenyl]-2'-yloxy)tantalum(V) chloride 、 Lithio-2,6-diphenylphenolat 以 苯 为溶剂， 生成 tris([1,1':3',1''-terphenyl]-2'-yloxy)tantalum(V) chloride
  参考文献：
  名称：

  空间上拥挤的芳氧基配体的化学反应-VII。2,6-二苯酚的一些第4族和第5族金属衍生物的合成，结构和光谱性质

  摘要：

  已经合成了一系列含有辅助配体2，6-二苯酚（OAr-2，6Ph 2）的早期过渡金属有机金属衍生物。化学计量的化合物Ti（OAr-2,6Ph 2）2（R）2（R = CH 3，CH 2 SiMe 3，CH 2 Ph和Ph）和Ti（OAr-2,6Ph）3（R）（R =通过用所需量的苯酚HOAr-2,6Ph 2处理相应的均烷基烷基TiR 4来获得CH 3，CH 2 SiMe 3）。对于第5组金属Nb和Ta，甲基衍生物M（OAr-2,6Ph 2）2（CH 3）3和M（OAr-2,6Ph 2）3（CH 3）2通过相应的氯-芳基氧化物的甲基化获得。除了常规的光谱表征外，二苯基Ti（OAr-2,6Ph 2）2（Ph）2和单烷基Ti（OAr-2,6Ph 2）3（CH 2 SiMe 3X射线衍射技术已在结构上对其进行了表征。这两个分子都围绕钛原子包含一个伪四面体环境，其短的1.794（3）–1.806（2）

  DOI：

  10.1016/s0277-5387(00)84541-6
• 作为产物：
  描述：

  tantalum pentachloride 、 2,6-二苯基苯酚 以 苯 为溶剂， 生成 bis([1,1':3',1''-terphenyl]-2'-yloxy)tantalum(V) chloride
  参考文献：
  名称：

  Intramolecular activation of aromatic C–H bonds by tantalum alkylidene groups: evaluating ‘cyclometallation resistant’ aryloxide ligation

  摘要：

  The ligands 2,3,5,6-tetraphenylphenoxide and 3,5-dimethyl-2,6-diphenylphenoxide undergo intramolecular aromatic C-H bond activation by tantalum alkylidene groups at rates 20 and 100 times slower than simple 2,6-diphenylphenoxide.

  DOI：

  10.1039/cc9960001973

文献信息

• Reactions of Alkynes and Olefins with Tantalum Hydrides Containing Aryloxide Ancillary Ligation:  Relevance to Catalytic Hydrogenation
  作者：Douglas R. Mulford、Janet R. Clark、Scott W. Schweiger、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/om990664l

  日期：1999.10.1

  [Ta(OC6H3Ph2-2,6)2(H)2Cl(PMe3)2] (1), [Ta(OC6H3Pri2-2,6)2(H)2Cl(PMe2Ph)2] (2), and [Ta(OC6H3But2-2,6)2(H)2Cl(PMePh2)] (3) toward olefins and alkynes has been investigated. The reactivity observed is highly dependent on the nature of the ancillary aryloxide ligands. The 2,6-diphenylphenoxide 1 reacts with styrene to produce 1 equiv of ethylbenzene and the styrene adduct [Ta(OC6H3Ph2-2,6)2(η2-CH2CHPh)Cl(PMe3)]

  三种氢化物的反应性[TA（OC 6 H 3 Ph 2 -2,6）2（H）2 Cl（PMe 3）2 ]（1），[TA（OC 6 H 3 Pr i 2 -2， 6）2（H）2 Cl（PMe 2 Ph）2 ]（2）和[TA（OC 6 H 3 Bu t 2 -2,6）2（H）2 Cl（PMePh 2）]（3已经研究了针对烯烃和炔烃的）。观察到的反应性高度依赖于辅助芳氧基配体的性质。2,6- diphenylphenoxide 1种发生反应与苯乙烯制备乙苯的1个当量和苯乙烯的加合物[TA（OC 6 H ^ 3博士2 -2,6）2（η 2 -CH 2 CHPh配合）氯（PME 3）] （ 5）。相反，1与3-己炔反应以消除H 2以及类似炔烃配合物6的形成。5和6的结构研究显示出具有沿Cl-TA-P轴分布的轴向烯烃（炔）单元的方锥几何结构。结构参数为这些分子提供了一个塔拉塔环丙烷（TAnTAlacyclopropene）键合图。化合物5在H
• Intramolecular activation of aromatic C–H bonds at tantalum(V) metal centers: evaluating cyclometallation ‘resistant’ and ‘immune’ aryloxide ligation
  作者：Jonathan S. Vilardo、Mark A. Lockwood、Linda G. Hanson、Janet R. Clark、Bernardeta C. Parkin、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1039/a702325a

  日期：——

  The trichloride compounds [Ta(OC 6 HPh 2 -2,6-R 2 -3,5)Cl 3 ] (1: R = H a, Ph b, Me c, Pr i d or Bu t e) have been obtained by treating [Ta 2 Cl 10 ] with the corresponding 3,5-disubstituted-2,6-diphenylphenols Ia–Ie. The solid-state structures of 1c and 1d show a square-pyramidal structure with an axial aryloxide ligand. The reaction of 1 with LiCH 2 SiMe 3 (3 equivalents) led to the isolation of the tris(alkyls) [Ta(OC 6 HPh 2 -2,6-R 2 -3,5) 2 (CH 2 SiMe 3 ) 3 ] (4a–4d) except in the case of the 3,5-di-tert-butyl derivative 1e which generated the alkylidene compound [Ta(OC 6 H 3 Ph 2 -2,6-Bu t -3,5) 2 (CHSiMe 3 )(CH 2 SiMe 3 )] 6e. The alkylidenes 6a–6d can be produced by photolysis of the corresponding tris(alkyls) 4a–4d. The alkylidenes 6a–6d undergo intramolecular cyclometallation of the aryloxide ligand (addition of an aromatic C–H bond to the tantalum alkylidene) at a rate which is extremely dependent on the meta substituents on the phenoxide nucleus. Kinetic studies show that conversion of 6a–6d into monometallated 7a–7d is first order with the phenyl, methyl and isopropyl substituents slowing the ring closure down by factors of 20, 90 and 360 respectively. The tert-butyl substituent completely shuts down cyclometallation of the adjacent phenyl ring. It is argued that bulky substituents inhibit rotation of the ortho-phenyl ring into a conformation necessary for C–H bond activation. Structural analysis of the torsion angles between ortho-phenyl and phenoxy rings has been carried out. The use of 1 H NMR chemical shifts has been demonstrated to be a valuable tool to probe the average conformations adopted in solution.

  通过将[Ta 2 Cl 10 ]与相应的 3,5-二取代-2,6-二苯基酚 IaâIe 处理，得到了三氯化物[Ta(OC 6 HPh 2 -2,6-R 2 -3,5)Cl 3 ]（1：R = H a、Ph b、Me c、Pr i d 或 Bu t e）。1c 和 1d 的固态结构显示出一种带有轴向芳氧基配体的方阵结构。1 与 LiCH 2 SiMe 3（3 个等价物）反应，分离出三（烷基）[Ta(OC 6 HPh 2 -2,6-R 2 -3,5) 2 (CH 2 SiMe 3 ) 3 ]（4aâ4d），但 3,5-二叔丁基衍生物 1e 除外，它生成了亚烷基化合物 [Ta(OC 6 H 3 Ph 2 -2,6-Bu t -3,5) 2 (CHSiMe 3 )(CH 2 SiMe 3 )] 6e。6e.通过光解相应的三烷基 4aâ4d 可以制得亚烷基 6aâ6d。亚烷基 6aâ6d 会发生芳氧基配体的分子内环金属化反应（在钽亚烷基上添加一个芳香族 CâH 键），反应速度与氧化酚核上的元取代基密切相关。动力学研究表明，6aâ6d 转化为单金属化 7aâ7d 的过程是一阶的，苯基、甲基和异丙基取代基会使闭环速度分别减慢 20、90 和 360 倍。叔丁基取代基完全阻止了邻近苯基环的环金属化。有观点认为，笨重的取代基抑制了正苯基环旋转到 CâH 键活化所需的构象。研究人员对正苯基环和苯氧环之间的扭转角进行了结构分析，结果表明，使用 1 H NMR 化学位移是探测溶液中平均构象的重要工具。
• Schweiger; Salberg; Pulvirenti, Journal of the Chemical Society, Dalton Transactions, 2001, # 13, p. 2020 - 2031
  作者：Schweiger、Salberg、Pulvirenti、Freeman、Fanwick、Rothwell

  DOI：——

  日期：——
• Mechanistic study of the cyclometalation of o-arylphenoxide ligands at Group 5 metal centers
  作者：Robert W. Chesnut、Gayatry G. Jacob、Joyce S. Yu、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/om00047a067

  日期：1991.1

  A series of 4-methylbenzyl derivatives of niobium and tantalum of general formula M(OAr)2-(CH2C6H4-4-Me)3 (OAr = various 2,6-diaryl- or 2,4,6-triarylphenoxides) have been synthesized. Thermolysis of these compounds at temperatures ranging from 100 to 150-degrees-C is found to lead to the elimination of 1 equiv of p-xylene and formation of a series of cyclometalated compounds in which intramolecular activation of the aromatic CH bond of one of the substituent aryl rings of an aryl oxide ligand had taken place. A mechanistic investigation of the reactivity was carried by utilizing 2,4,6-triarylphenoxide groups in which the 2-aryl group contained the para substituent CH3, CH3O, and Cl. The product distribution of these competitive ring-closure reactions was estimated by using H-1 NMR spectroscopy. The effect of substituents within the aryl ring upon the rate of ring closure was found to be slight. It was found, however, that irrespective of whether an electron-donating (CH3) or electron-withdrawing (Cl) substituent was used the substituted ring underwent metalation preferentially over the nonsubstituted ring. The results of this study are inconsistent with these reactions following an electrophilic aromatic substitution pathway proceeding via an arenium ion intermediate being operative for these reactions. A structural study of the tris(4-methylbenzyl) substrates M(OC6H3Ph2-2,6)2(CH2C6H4Me)3 (M = Nb, Ta) showed the compounds to be isomorphous in the solid state with trans, axial aryl oxide ligands and three equatorial 4-methylbenzyl groups about the metal center. Crystal data at 22-degrees-C for Nb(OC6H3Ph2-2,6)2(CH2C6H4Me)3 are as follows: a = 13.008 (3) angstrom, b = 14.356 (3) angstrom, c = 15.235 (2) angstrom, alpha = 105.49 (1)-degrees, beta = 100.98 (1)-degrees, gamma = 91.46 (2)-degrees, Z = 2, d(calcd) = 1.227 g cm-3 in space group P1BAR. Crystal data for Ta(OC6H3Ph2-2,6)2(CH2C6H4Me)3 at 20-degrees-C are as follows: a = 12.982 (2) angstrom, b = 14.348 (2) angstrom, c = 15.210 (5) angstrom, alpha = 105.49 (2)-degrees, beta = 100.81 (2)-degrees, gamma = 01.36 (2)-degrees, Z = 2, d(calcd) = 1.341 g cm-3 in space group P1BAR. Both compounds contain one toluene solvate molecule per metal.
• Chesnut, Robert W.; Steffey, Bryan D.; Rothwell, Ian P., Polyhedron, 1988, vol. 7, p. 752 - 756
  作者：Chesnut, Robert W.、Steffey, Bryan D.、Rothwell, Ian P.、Huffman, John C.

  DOI：——

  日期：——