Ta(2,6-diphenylphenoxide)2(4-methylbenzyl)3 | 119705-31-6

• 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: Ta(2,6-diphenylphenoxide)2(4-methylbenzyl)3
• CAS: 119705-31-6
• 化学式: C₆₀H₅₃O₂Ta
• 分子量: 987.028
• InChiKey: HXLBZEOYMQDUBG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  15.86
• 重原子数：
  63.0
• 可旋转键数：
  14.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  Ta(2,6-diphenylphenoxide)2(4-methylbenzyl)3 以 氘代甲苯 为溶剂， 生成 Ta(OC6H4(C6H5)C6H4)(2,6-diphenylphenoxide)(4-methylbenzyl)2
  参考文献：
  名称：

  Mechanistic study of the cyclometalation of o-arylphenoxide ligands at Group 5 metal centers

  摘要：

  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.

  DOI：

  10.1021/om00047a067
• 作为产物：
  描述：

  Mg(4-methylbenzyl)2 、 bis([1,1':3',1''-terphenyl]-2'-yloxy)tantalum(V) chloride 生成 Ta(2,6-diphenylphenoxide)2(4-methylbenzyl)3
  参考文献：
  名称：

  Chesnut, Robert W.; Steffey, Bryan D.; Rothwell, Ian P., Polyhedron, 1988, vol. 7, p. 752 - 756

  摘要：

  DOI：

文献信息

• Isolation of a new series of seven-coordinate hydride compounds of tantalum(V) and their involvement in the catalytic hydrogenation of arene rings
  作者：Bernardeta C. Ankianiec、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/ja00012a066

  日期：1991.6
• Synthesis and Characterization of a Series of Mononuclear Tantalum(V) Hydride Compounds Containing Aryloxide Ligation
  作者：Bernardeta C. Parkin、Janet R. Clark、Valerie M. Visciglio、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/om00006a051

  日期：1995.6

  A series of seven-coordinate, mononuclear tantalum-hydride compounds [Ta(OC6H3Pr2i-2,6)(2)-(Cl)(3-n)(H)(n)](1, n = 1; 2, n = 2; 3, n = 3; OC6H3Pr2i-2,6 = 2,6-diisopropylphenoxide; L = tertiary phosphines) can be obtained either by hydrogenolysis of the corresponding tantalum alkyl substrate, producing 2 and 3, or by reacting the trichloride [Ta(OC6H3Pr2i-2,6)(2)Cl-3] with one (for 1) or two (for 2) equiv of Bu(3)(n)SnH in the presence of ligand. The hydrogenolysis of the substrate [Ta(OC6H3Pr2i-2,6)(2)(CH2C6H4-4Me)(3)] in the presence of PMe(2)Ph or PMePh(2) produces the complexes [Ta(OC6H3Pr2i-2,6)(2)(H)(3)(L)(2)] (3a, L = PMe(2)Ph; 3b, L = PMePh(2)), while the compounds [Ta(OC(6)H(3)Ph(2)-2,6)(2)(R)(3)] (R = CH2C6H4-4Me, CH(2)SiMe(3)) produce [Ta(OC(6)H(3)Cy(2)-2,6)(2)(H)(3)(L)(2)] (3c, L = PMe(2)Ph; 3d, L = PMePh(2)) with the 2,6-dicyclohexylphenoxide ligand being generated by intramolecular hydrogenation of the ortho phenyl rings in the 2,6-diphenylphenoxide substrate. The hydrogenolysis of the bisalkyl [Ta(OC6H3Pri(2)-2,6)(3)(CH2C6H4-4Me)(2)] in the presence of PMe(2)-Ph produces the six-coordinate [Ta(OC6H3Pr2i-2,6)(3)(PMe(2)Ph)(H)(2)], 4b, which will exchange the phosphine ligand to produce a series of substituted derivatives. A related series of six-coordinate dihydride compounds [Ta(OC(6)H(3)Bu(2)(t)-2,6)(2)(L)(Cl)(H)(2)], 5, are produced by addition of Bu(n)SnH (2 Sn per Ta) to [Ta(OC(6)H(3)Bu(t)(2)-2,6)(2)Cl-3] in the presence of added L. Single-crystal X-ray diffraction analyses of seven-coordinate 1, 2b, and 3c (all cases L = PMe(2)Ph) show them to adopt pentagonal bipyramidal geometries with traits axial aryloxide ligands. In monohydride 1 the unique hydride ligand is cis to both phosphine ligand, while in dihydride 2b the hydride ligands are mutually cis but trans to the chloride group within the pentagonal plane. A crystallographic 2-fold axis in trihydride 3c passes through the unique Ta-H bond and bisects the remaining cis hydride ligands within the pentagonal plane. The solution H-1 NMR spectra of 1, 2, and 3 are consistent with the solid state structure being maintained in solution. Furthermore, analysis and simulation of the downfield hydride resonances in 2 and 3 show these seven-coordinate molecules to be stereochemically rigid on the NMR time scale. The coupling constants obtained from simulations conclusively rule out the formulation of 2 or 3 as containing eta(2)-H-2 ligands. The solid state structures of six-coordinate [Ta(OC6H3Pri(2)-2,6)(3)(PMe(2)Ph)(H)(2)], 4b, and [Ta(OC(6)H(3)Bu(2)(t)-2,6)(2)- (PMePh(2))(Cl)(H)(2)], 5c, show a geometry severely distorted from octahedral.In both compounds the mutually trans hydride ligands are bent toward the phosphine ligand with H-Ta-P angles of 66(2)degrees and 69(1)degrees for 4a and 56(2)degrees and 62(2)degrees for 5b. A steric origin to this distortion is ruled out by the structure of 5b in which the hydride ligands are bent toward the bulky phosphine ligand and away from the Ta-Cl bond. Strong support for the distorted structures of 4 and 5 comes from solution and solid state infrared spectra where two sharp <(nu)over bar>(Ta-H) vibrations are observed. Analysis ofthe intensity ratio for the symmetric and asymmetric bands yields predicted H-Ta-H angles very close to these observed in the solid state structure. The summary of the crystal data is as follows for [Ta(OC6H3Pr2i-2,6)(2)(PMe(2)Ph)(2)(Cl)(2)(H)], 1, at 20 degrees C: a = 26.025(4) Angstrom, b = 10.7954(5) Angstrom, c = 18.509(3) Angstrom, beta = 128.31(1)degrees, Z = 4, d(calcd) = 1.438 g cm(-3) in space group C2/c. For [Ta(OC6H3Pr2i-2,6)(2)(PMe(2)Ph)(2)(Cl)(H)(2)], 2b, at 20 degrees C: a = 9.735(1) Angstrom, b = 24.310(3) Angstrom, c = 17.735(2) Angstrom, beta = 90.76(1)degrees, Z = 4, d(calcd) = 1.344 g cm(-3) in space group P2(1)/n. For [Ta(OC(6)H(3)Cy(2)-2,6)(2)(PMe(2)Ph)(2)(H)(3)], 3c, at 20 degrees C: a = 24.065(3) Angstrom, b = 13.530(2) Angstrom, c = 20.263(3) Angstrom , beta = 131.633(9)degrees, Z = 4, d(calcd) = 1.313 g cm(-3) in space group C2/c. For [Ta(OC6H3Pr2i-2,6)(3)(PMe(2)Ph)(H)(2)], 4b, at 20 degrees C: a = 10.637(1) Angstrom, b = 12.820(2) Angstrom, c = 31.799(4) Angstrom, beta = 98.76(1)degrees, Z = 4, d(calcd) = 1.322 g cm(-3) in space group P2(1)/n. For [Ta(OC(6)H(3)But(2)-2,6)(2)(PMePh(2))(Cl)(H)(2)], 5c, at -100 degrees C, a = 10.851(5) Angstrom, b = 18.110(7) Angstrom, c = 20.09(1) Angstrom, beta = 96.67(5)degrees, Z = 4, d(calcd) = 1.404 g cm(-3) in space group P2(1)/n.