[(η5-C5H5)Ti(OC6H3(i-Pr)2-2,6)Me2] | 256394-28-2

• 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: [(η5-C5H5)Ti(OC6H3(i-Pr)2-2,6)Me2]
• 英文别名: [(C5H5)Ti(OC6H3i-Pr)2-2,6)Me2]；carbanide;cyclopenta-1,3-diene;2,6-di(propan-2-yl)phenolate;titanium(4+)
• CAS: 256394-28-2
• 化学式: C₁₉H₂₈OTi
• 分子量: 320.311
• InChiKey: UIXHUHWFLWOEIC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(η5-C5H5)Ti(OC6H3(i-Pr)2-2,6)Me2] 、 三(五氟苯基)硼烷 以 氘代甲苯 为溶剂， 生成 [(η5-C5H5)Ti(OC6H3(i-Pr)2-2,6)Me][MeB(C6F5)3]
  参考文献：
  名称：

  Diverse Pathways of Activation and Deactivation of Half-Sandwich Aryloxide Titanium Polymerization Catalysts

  摘要：

  A series of half-sandwich aryloxide titanium complexes, [CpTi(OAr)Me-2] (CP = C5H5; OAr = OC6H3-Me-2-2,6, OC6H3Et2-2,6, (OC6H3Pr2)-Pr-i-2,6, (OC6H3Pr2)-Pr-t-2,6, and OC6HPh4-2,3,5,6), have been synthesized. These compounds react with B(C6F5)(3) to give thermally unstable complexes [CpTi(OAr)Me][MeB(C6F5)(3)]. Two different deactivation pathways have been identified within the series. The tetraphenylphenoxide, cationic methyl compound decomposes cleanly at room temperature to give [CpTi(OC6HPh4-2,3,5,6)(C6F5){CH2B(C6F5)(2)}] and methane with a first-order rate constant of 7.6(2) x 10(-4) s(-1) at 25 degrees C. For relatively smaller aryloxide ligands, OAr = (OC6H3Pr2)-Pr-i-2,6, (OC6H3Bu2)-Bu-t-2,6, a Me/C6F5 exchange takes place, yielding CpTi(OAr)Me(C6F5) and MeB(C6F5)(2). The cationic titanium complexes are shown to be active for the polymerization of 1-hexene. At -20 and 0 degrees C, first-order dependence on the concentration of 1-hexene is observed. The rate of polymerization decreases with increasing steric hindrance of aryloxides except for OAr = OC6HPh4-2,3,5,6.

  DOI：

  10.1021/om0507272
• 作为产物：
  描述：

  CpTi(OC6H3-2,6-i-Pr2)2Cl 、 三甲基铝 以 氘代苯 、 甲苯 为溶剂， 生成 [(η5-C5H5)Ti(OC6H3(i-Pr)2-2,6)Me2]
  参考文献：
  名称：

  Ancillary aryloxide ligands in ethylene polymerization catalyst precursors

  摘要：

  The compounds CpTiCl2(OC6H3-i-Pr-2) (1), CpTiCl(OC6H3-i-Pr-2)(2) (2), CpTi(R)(OC6H3-i-Pr-2)(2) (R = t-Bu 3, s-Bu 4, n-Bu 5, Me 6) have been prepared and characterized. Compounds 1 or 2 in the presence of 500 equivalents of methylaluminoxane (MAO) act as catalyst precursors for ethylene polymerization. While the catalysts derived from the monocyclopentadienyl complexes are much less active that the metallocenes, there is a clear enhancement in the activity of about 40% as a result of the inclusion of a second aryloxide ligand. Reactions of 1 with AlMe3 revealed stepwise formation of CpTi(Me)Cl(OC6H3-i-Pr-2) 7 and CpTi(Me)(2)(OC6H3-i-Pr-2) 8, while subsequent addition of AlMe3 afforded complete conversion to 8, with formation of the aluminum species [AlMe2(OC6H3-i-Pr-2)](n) 9. In contrast, the catecholate complex CpTi(O2C6H4)Cl 10 reacts with AlMe3 yielding the paramagnetic species [CpTi(O-2(C6H4)). AlClMe2], 11. Incorporation of aryloxide ligands in modified metallocenes was readily accomplished with the preparation of Cp2ZrCl(OC6H3-i-Pr-2) 12, Cp2ZrCl(OC6H5) 13, Cp2ZrMe(OC6H5) 14 and Cp2TiCl(OC6H3-i-Pr-2) 15. In combination with MAO, 12, 14 and 15 effect the polymerization of ethylene with an 11% increase in activity over the parent metallocenedichlorides. The implications of the increased activity are considered. Crystallographic data are reported for 2, 3, 6, 9, 11, 12 and 13. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00422-2

文献信息

• Formation of Neutral and Cationic Methyl Derivatives of Titanium Containing Cyclopentadienyl and Aryloxide Ancillary Ligation
  作者：Andrew E. Fenwick、Khamphee Phomphrai、Matthew G. Thorn、Jonathan S. Vilardo、Christine A. Trefun、Brigitte Hanna、Phillip E. Fanwick、Ian P. Rothwell

  DOI：10.1021/om0341404

  日期：2004.4.1

  [CpTi(OAr)Me][MeB(C6F5)3]. The compound [CpTi(OC6HPh4-2,3,5,6)Me][MeB(C6F5)3] (27) was studied via solution VT-NMR spectroscopy, and the free energy of activation for methyl exchange was estimated to be 14.4(5) kcal mol-1 at 10 °C. These thermally unstable cationic derivatives readily eliminate methane at room temperature, affording compounds of the type [CpTi(OAr)(C6F5)CH2B(C6F5)2}]. A kinetic study

  通过[CpTi（OAr）Cl 2 ]与2的反应制备了一系列由一个环戊二烯基（Cp）和一个2,6-二取代的芳氧基（OAr）连接的二甲基钛化合物[CpTi（OAr）Me 2 ]。当量的LiMe或通过将母体苯酚（HOAr）添加到[CpTiMe 3 ]的冷醚溶液中。该化合物是稳定的，除了那些含有较小体积的邻甲基取代基的化合物以外。化合物[CpTi（OC 6 H 2 Me 2 -2,6-X-4）Me 2 ]（X = H（19），Br（20））进行配体交换以产生[CpTi（OC 6 H 2 Me 2 -2,6-X-4）2 Me]（X = H（22），Br（23））和[CpTiMe 3 ]。已获得二甲基化合物[CpTi（OC 6 H 2 Np-2-Bu t 2 -4,6）Me 2 ]（13），[CpTi（OC 6 H 2 C 10 H 9） } -2-卜吨2 -4,6-）Me 2 ]（14），的[Cp
• Structure−Activity Correlation in Titanium Single-Site Olefin Polymerization Catalysts Containing Mixed Cyclopentadienyl/Aryloxide Ligation
  作者：Thomas A. Manz、Khamphee Phomphrai、Grigori Medvedev、Balachandra B. Krishnamurthy、Shalini Sharma、Jesmin Haq、Krista A. Novstrup、Kendall T. Thomson、W. Nicholas Delgass、James M. Caruthers、Mahdi M. Abu-Omar

  DOI：10.1021/ja0640849

  日期：2007.4.1

  In this work, we report the synthesis of eighteen titanium cyclopentadienyl aryloxide complexes and their propagation rate constants for 1-hexene polymerization. A correlation between k(p) values and the underlying catalyst structures is developed using DFT-computed ligand cone angles and ion pair separation energies as structural and electronic descriptors. The correlation takes the form of an Arrhenius-like relationship where the pre-exponential factor is correlated to the ligand cone angles and the activation energy term is correlated to the ion pair separation energies. This finding is consistent with the idea that the ability of the monomer to access the metal center is a key factor affecting the reaction rate.