(η(5)-C5Me5)TiMe2(Cl) | 117527-00-1

• 英文名称: (η(5)-C5Me5)TiMe2(Cl)
• 英文别名: (η5-Cp*)TiClMe2；Cp*TiMe2Cl；(C5(CH3)5)TiMe2Cl；[TiCl(pentamethylcyclopentadienyl)(Me)2]
• CAS: 117527-00-1
• 化学式: C₁₂H₂₁ClTi
• 分子量: 248.632
• InChiKey: QOZBYFVNNOAAHR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η(5)-C5Me5)TiMe2(Cl) 、 五氟苯锂 以 乙醚 、 正己烷 为溶剂， 以58%的产率得到(η(5)-C5Me5)TiMe2(C6F5)
  参考文献：
  名称：

  一系列新型的高度亲电的单环戊二烯基钛烯烃聚合引发剂的合成

  摘要：

  我们合成了新化合物 Ti(η-C 5 Me 5 )Me 2 E (E = C 6 F 5 或 OC 6 F 5 ) 和 Ti(η-C 5 Me 5 )Me(OC 6 F 5 ) 2，并通过 47/49 Ti NMR 光谱等多种技术对其进行了表征。所有这三种化合物都与硼烷 B(C 6 F 5 ) 3 发生反应，形成高度亲电但热不稳定的物种 Ti(η-C 5 Me 5 )Me(E)(µ-Me)B(C 6 F 5 ) 3 和[(η-C 5 Me 5 )Ti(OC 6 F 5 ) 2 ][BMe(C 6 F 5 ) 3 ]，对其溶液结构和动力学进行了研究，并与已知化合物 Ti(η-C 5 Me 5 )Me 2 (µ-Me)B(C 6 F 5 ) 3 的溶液结构和动力学进行了比较。有趣的是，Ti(η-C 5 Me 5 )Me(C 6 F 5 )( µ-Me)B(C 6 F 5 ) 3 既没有明显的离子对解离成溶剂分离离子 [(η-C 5 Me 5 )TiMe(C 6 F 5 )] + 和 [BMe(C 6 F 5 ) 3 ] - 也没有明显的硼烷解离成其前体 (η-C 5 Me 5 )TiMe 2 (C 6 F 5 ) 和 B(C 6 F 5 ) 3 ；事实上，在核磁共振时间尺度上，围绕 Ti-C 6 F 5 键的旋转和手性金属的反转都很缓慢。相比之下，Ti(η-C 5 Me 5 )Me(OC 6 F 5 )( µ-Me)B(C 6 F 5 ) 3 的易变性更高，与 Ti(η-C 5 Me 5 )Me 2 (µ-Me)B(C 6 F 5 ) 3 一样，也会发生离子对解离、而[(η-C 5 Me 5 )Ti(OC 6 F 5 ) 2 ][BMe(C 6 F 5 ) 3 ]在溶液中作为溶剂分离的离子物种[(η-C 5 Me 5 )Ti(OC 6 F 5 ) 2 ]+ 和[BMe(C 6 F 5 ) 3 ]- 与其前体(η-C 5 Me 5 )TiMe(OC 6 F 5 ) 2 和 B(C 6 F 5 ) 3 处于平衡状态。

  DOI：

  10.1039/a703112b
• 作为产物：
  描述：

  (五甲基环戊二烯基)三氯化钛(IV) 、 甲基锂 以 正己烷 为溶剂， 以85%的产率得到(η(5)-C5Me5)TiMe2(Cl)
  参考文献：
  名称：

  Mena, Miguel; Royo, Pascual; Serrano, Ricardo, Organometallics, 1989, vol. 8, # 2, p. 476 - 482

  摘要：

  DOI：

文献信息

• Preparation and Characterization of Half-Sandwich (Pentamethylcyclopentadienyl)(triflato)titanium(IV) Complexes: Solid-State Structural Motifs and Catalysis Studies
  作者：Silvana C. Ngo、Paul J. Toscano、John T. Welch

  DOI：10.1002/1522-2675(200210)85:10<3366::aid-hlca3366>3.0.co;2-y

  日期：2002.10

  Half-sandwich (pentamethylcyclopentadienyl)(triflato)titanium(IV) complexes of the type [Ti(Cp*)(TfO)2X] (X=MeO (1), Me (2), 2,4,6-Me3C6H2O (5)) or [Ti(Cp*)(o-OC6H4O)(TfO)] (7) were readily synthesized via methathesis of the corresponding chloride complexes with silver triflate (Cp*=(η5-1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl)). In addition, the complex 3 with X=OH was prepared by controlled hydrolysis

  [Ti(Cp*)(TfO)2X] (X=MeO (1), Me (2), 2,4,6-Me3C6H2O (5 )) 或 [Ti(Cp*)(o-OC6H4O)(TfO)] (7) 很容易通过相应的氯化物配合物与三氟甲磺酸银的复分解合成 (Cp*=(η5-1,2,3,4,5) -pentamethylcyclopenta-2,4-dien-1-yl))。此外，通过控制水解2制备了具有X=OH的配合物3。这些新配合物的固态结构是通过单晶X射线衍射技术确定的。确定了三种不同的结构基序；1、2、3 和 7 是二聚体，而 5 是单体。筛选配合物在均相条件下立体有择聚合苯乙烯的能力。在没有活化剂如 MAO（甲基铝氧烷）的情况下，1和2容易催化无规立构聚苯乙烯的形成；注意到对 X 的空间大小有很强的依赖性。在 MAO 的存在下，所有的配合物都表现出高活性和对间规聚苯乙烯合成的强烈偏好，优于 [TiCl3(Cp*)]/MAO。
• Ethylene and Propylene Polymerization by a Series of Highly Electrophilic, Chiral Monocyclopentadienyltitanium Catalysts
  作者：Sean W. Ewart、Mark J. Sarsfield、Dusan Jeremic、Tracey L. Tremblay、Edan F. Williams、Michael C. Baird

  DOI：10.1021/om970522w

  日期：1998.4.1

  (C6F5)3, Cp*TiMe(OC6F5)(μ-Me)B(C6F5)3, and Cp*TiMeCl(μ-Me)B(C6F5)3, respectively, which are similar to the known Cp*TiMe2(μ-Me)B(C6F5)3. All four μ-Me compounds behave as sources of the highly electrophilic species [Cp*TiMeE]+ (E = Me, Cl, C6F5, OC6F5) when treated with the borane, the last three being chiral, and all four systems exhibit catalytic activities for the polymerization of ethylene to

  化合物的CP *时间2 ç 6 ˚F 5中，CP *时间2 OC 6 ˚F 5和CP *时间2 Cl（上的CP * =η 5 -C 5我5）与硼烷乙反应（C 6 ˚F 5）3形成热不稳定的手性络合物CP * TiMe（C 6 F 5）（μ-Me）B（C 6 F 5）3，CP * TiMe（OC 6 F 5）（μ-Me）B（C 6 F 5）3和CP * TiMeCl（μ-Me）B（C6 F 5）3分别类似于已知的CP * TiMe 2（μ-Me）B（C 6 F 5）3。所有四种μ-Me化合物均表现为高度亲电物种[CP * TiMeE] +（E = Me，Cl，C 6 F 5，OC 6 F 5当用硼烷处理时，最后三个是手性的，并且所有四个体系都表现出催化活性，使乙烯聚合成高分子量聚乙烯。尽管三种化合物在钛上具有手性，但所有这些化合物的丙烯聚合都会导致形成无规立构的弹性聚丙烯。形成的丙烯聚合物的NMR分析表明，引发过程涉及将1
• Ethylene and propylene polymerization by cationic monocyclopentadienyl titanium catalysts containing the weakly coordinating anion [B(C6F5)4]−
  作者：Sean W Ewart、Mark J Sarsfield、Edan F Williams、Michael C Baird

  DOI：10.1016/s0022-328x(98)01209-1

  日期：1999.5

  systems does not generally result in catalysts exhibiting lower activities and producing lower molecular weight polymers. An EPR study of the Cp*TiMe3/[Ph3C][B(C6F5)4] system in chlorobenzene at room temperature indicates that <0.01% of the titanium is present occasionally during polymerization as a complex of titanium(III), suggesting that a contribution to the catalytic processes by titanium(III) species

  化合物的Cp *时间2 E（*的Cp =η 5 -C 5我5 ; E =我，C 6 ˚F 5，OC 6 ˚F 5，Cl）的具有三苯甲基四反应（全氟苯基）硼酸盐，[PH 3 C] [ B（C 6 F 5）4 ]形成热不稳定的二钛配合物[（Cp * TiMeE）2（μ-Me）] [B（C 6 F 5）4 ]，所有这些都作为高价金属的来源亲电物质[Cp * TiMeE] +。这些[B（C 6 F 5）的活性的调查4 ] -作为乙烯和丙烯聚合催化剂的盐表明，它们比类似化合物Cp * TiMeE（μ-Me）B（C 6 F 5）3更具活性，这是因为[B（C 6 F 5）4 ] -是比[BMe（C 6 F 5）3 ] -更差的配体。然而，与目前所认为的智慧相反，[Cp * TiMe 2 ] +的甲基配体被更多的吸电子C 6 F 5，OC 6 F 5取代这些单环戊二烯基体系中的C 1和C 1配体通常不会导
• Solution structures and exchange phenomena of the new alkene polymerization initiators (η-C5Me5)TiMe(E)(μ-Me)B(C6F5 )3 (E = C6F5, OC6F5) and [(η-C5Me5)Ti(OC6F5)2 ][BMe(C6F5)3]
  作者：Tracey L. Tremblay、Sean W. Ewart、Mark J. Sarsfield、Michael C. Baird

  DOI：10.1039/a700232g

  日期：——

  The solution structures and dynamics of the new alkene polymerization initiators (η-C 5 Me 5 )TiMe(C 6 F 5 )(µ- Me)B(C 5 F 5 ) 3 2, (η-C 5 Me 5 )TiMe(OC 6 F 5 )(µ -Me)B(C 6 F 5 ) 3 3 and [(η-C 5 Me 5 )Ti(OC 6 F 5 ) 2 ][BMe(C 5 F 5 ) 3 ] 4 are compared and contrasted with those of the known initiator (η-C 5 Me 5 )TiMe 2 (µ-Me)B(C 6 F 5 ) 3 1; compound 2 undergoes neither spontaneous ion-pair dissociation to the solvent separated [(η-C 5 Me 5 )TiMe(C 6 F 5 )] + and [BMe(C 6 F 5 ) 3 ] - nor borane dissociation to its precursors (η-C 5 Me 5 )TiMe 2 (C 6 F 5 ) and B(C 6 F 5 ) 3 ; in contrast, 3 is more labile and does undergo ion-pair dissociation, while 4 exists in solution as the separated ion species in equilibrium with its precursors, (η-C 5 Me 5 )TiMe(OC 6 F 5 ) 2 and B(C 6 F 5 ) 3 .

  分解，但3的稳定性较差，会发生离子对分解。
• 13C-NMR study of Ti(IV) species formed by Cp*TiMe3 and Cp*TiCl3 activation with methylaluminoxane (MAO)
  作者：Konstantin P. Bryliakov、Nina V. Semikolenova、Vladimir A. Zakharov、Evgenii P. Talsi

  DOI：10.1016/s0022-328x(03)00232-8

  日期：2003.10

  Using C-13- and H-1-NMR spectroscopy, titanium(IV) species formed in the catalytic systems Cp*TiMe3/MAO and Cp*TiCl3/MAO (Cp* = C-5(CH3)(5)) in toluene and chlorobenzene were studied within the temperature range 253-293 K and at Al/Ti ratios 30-300. It was shown that upon activation of Cp*TiMe3 with methylaluminoxane (MAO) mainly the 'cation-like' intermediate Cp*Me2Ti+ <-- Me- -Alequivalent to(MAO) (2) is formed. Three types of titanium(IV) complexes were identified in Cp*TiCl3/MAO catalytic system. They are methylated complexes Cp*TiMeCl2 and Cp*TiMe2Cl, and the 'cation-like' intermediate 2. Complex 2 dominates in Cp*TiCl3/MAO system in conditions approaching to those of practical polymerization (Al/Ti ratios more than 200). According to the EPR measurements, the portion of EPR active Ti(III) species in the Cp*TiCl3/MAO system is smaller than 1% at Al/Ti = 3 5, and is about 10% at Al/Ti = 700. (C) 2003 Elsevier Science B.V. All rights reserved.