[(η5-C5H5)Ti(OC6H3(Et)2-2,6)Me][MeB(C6F5)3] | 935842-28-7

• 英文名称: [(η5-C5H5)Ti(OC6H3(Et)2-2,6)Me][MeB(C6F5)3]
• 英文别名: [CpTi(OC6H3-2,6-Et2)Me][MeB(C6F5)3]
• CAS: 935842-28-7
• 化学式: C₁₆H₂₁OTi*C₁₉H₃BF₁₅
• 分子量: 804.242
• InChiKey: HICZNYWYGJIDNC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  [(η5-C5H5)Ti(OC6H3Et2-2,6)Me2] 、 三(五氟苯基)硼烷 以 氘代甲苯 为溶剂， 生成 [(η5-C5H5)Ti(OC6H3(Et)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

文献信息

• 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.