[(η5-C5Me5)TiCl2(NP((CH3)3C)3)] | 532434-80-3

• 英文名称: [(η5-C5Me5)TiCl2(NP((CH3)3C)3)]
• 英文别名: Cp(*)((t)Bu3P=N)TiCl2
• CAS: 532434-80-3
• 化学式: C₂₂H₄₂Cl₂NPTi
• 分子量: 470.342
• InChiKey: IBAHYRQXLBFYMC-UHFFFAOYSA-L

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：

  [(η5-C5Me5)TiCl2(NP((CH3)3C)3)] 在 三乙基铝 作用下， 以 正己烷 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Catalyst systems containing low valent titanium compounds and polymers produced therefrom

  摘要：

  本文公开了一种从半茂钛化合物和烷基铝化合物合成低价双金属钛化合物的方法。这些双金属钛化合物可以用作催化剂体系中的组分，用于烯烃聚合。

  公开号：

  US10000595B1
• 作为产物：
  描述：

  (五甲基环戊二烯基)三氯化钛(IV) 、 N-Trimethylsilyl-tri(tert.-butyl)phosphinimin 以 苯 为溶剂， 以73%的产率得到[(η5-C5Me5)TiCl2(NP((CH3)3C)3)]
  参考文献：
  名称：

  一种催化剂设计方法：乙烯聚合中的环戊二烯基膦亚胺钛配合物

  摘要：

  基于庞大的膦酰亚胺与环戊二烯基配体的空间和电子类比，开发了一种聚合催化剂设计策略。为此，制备并表征了 (Cp†)TiCl2(NPR3) 形式的配合物家族。还合成了这些物质的烷基和芳基衍生物，并且已经评估了一些在烯烃聚合中用作催化剂前体。已经使用几种类型的助催化剂活化剂检查了乙烯的聚合。讨论了构效关系的趋势和模式，并评估了对催化剂设计的影响。

  DOI：

  10.1021/om020954t

文献信息

• Toluene and α-Olefins as Radical Scavengers: Direct NMR Evidence for Homolytic Chain Transfer Mechanism Leading to Benzyl and “Dormant” Titanium Allyl Complexes
  作者：Francesco Zaccaria、Cristiano Zuccaccia、Roberta Cipullo、Peter H. M. Budzelaar、Alceo Macchioni、Vincenzo Busico、Christian Ehm

  DOI：10.1021/acs.organomet.8b00755

  日期：2018.11.26

  Resting/dormant benzyl- and allyl-type Ti(IV) complexes formed under α-olefin polymerization conditions have been detected and characterized by NMR. Experimental and computational evidence supports a formation mechanism via reversible Ti–C bond homolysis rather than “classical” σ-bond metathesis.

  已经检测到在α-烯烃聚合条件下形成的静止/休眠的苄基和烯丙基型Ti（IV）配合物，并通过NMR进行了表征。实验和计算证据支持通过可逆的Ti-C键均质而不是“经典”σ键复分解的形成机理。
• Reduction of Titanium(IV)-Phosphinimide Complexes:  Routes to Ti(III) Dimers, Ti(IV)-Metallacycles, and Ti(II) Species
  作者：Todd W. Graham、James Kickham、Silke Courtenay、Pingrong Wei、Douglas W. Stephan

  DOI：10.1021/om049826q

  日期：2004.6.1

  achieved upon reduction of Cp‘Ti(t-Bu2(2-C6H4Ph)PN)Cl2 (Cp‘ = Cp 18, Cp* 19). The products [Cp‘Ti(NPtBu2(2-C6H4Ph)] (Cp‘ = Cp 20, Cp* 21) contained η6-interactions between Ti and the 2-phenyl substituent of the biphenyl unit. While Ti(II)-phosphinimide complexes have proven difficult to handle due to their reactivity, an unequivocal example of a Ti(II) species was obtained via reduction of Cp*Ti(NPt-Bu3)Cl2

  已经研究了含次膦酰亚胺的IV族金属配合物的氧化还原化学。简单phosphinimide物种的CPa href=https://www.molaid.com/MS_154274 target="_blank">PTI（NPR的反应3）氯2（R =我1，我-Pr 2）用Mg，得到复合物配制成[CPa href=https://www.molaid.com/MS_154274 target="_blank">PTiCl（μ-NPR 3）] 2（R =我3，异-镨4）。相反，CPa href=https://www.molaid.com/MS_154274 target="_blank">PTi（NP t -Bu 3）Cl 2（5Mg将其还原为推定的Ti（II）物种，该物种可以被各种试剂拦截，包括2,3-二甲基-1,3-丁二烯，联苯乙炔，苯乙炔，双（三甲基甲硅烷基）乙炔，乙烯和丙烯给出单金属金属环配合物。以这种方式，在Ti（IV）metallacycles的CPa href=https://www.molaid.com/MS_154274 target="_blank">PTI（NP叔卜3）（CH 2 C（Me）的C（Me）的CH 2），6，CPTI（NP叔卜3）（CPH）4，7，的CPa href=https://www.molaid.com/MS_154274 target="_blank">PTI（NP叔卜3）（C（PH）CHC（PH）CH），8，CPTI（NP叔卜3）（η 2 -C 2（森达3）2），9，CPTI（NP叔卜3）（CH 2）4，10，CPTI（NP叔卜3）（CH
• Competitive ArC−H and ArC−X (X = Cl, Br) Activation in Halobenzenes at Cationic Titanium Centers
  作者：Kuangbiao Ma、Warren E. Piers、Masood Parvez

  DOI：10.1021/ja0583618

  日期：2006.3.1

  The titanium methyl cation [Cp*((Bu3P)-Bu-t=N)TiCH3](+)[B(C6F5)(4)](-) reacts rapidly with H-2 to give the analogous cationic hydride [Cp*((Bu3P)-Bu-t=N)TiH(THF)(n)](+)[B(C6F5)(4)](-) (n = 0, 1), which can be trapped and isolated as its THF adduct 1 (.) THF (n = 1). When generated in the presence of chloro or bromobenzene, 1 undergoes C-X activation or ortho-C-H activation, depending on the amount of dihydrogen present in the reaction medium. At similar to 4 atm of H-2, C-X activation is preferred, giving the halocations [Cp*((Bu3P)-Bu-t=N)TiX](+)[B(C6F5)(4)](-) (2X) and C6H6/biphenyl mixtures. At lower pressures of H-2 (> 1 atm), the beta-halophenyl cations [Cp*((Bu3P)-Bu-t=N)Ti(2-X-C6H4)](+)[B(C6F5)(4)](-) (3X) are the products isolated. In the absence of H-2, these compounds are quite thermally stable, but undergo beta-halogen elimination upon moderate heating, to give 2X (similar to 20%) and compounds U which are the result of reaction between 2X and benzyne via addition of the benzyne C-C triple bond across the Ti-N bond of the phosphinimide ligand. Thus, three separate bond activation processes are operative in this system: direct C-X activation, ortho-C-H activation, and indirect C-X activation via beta-halogen elimination. Mechanistic studies on all three processes have been done and support a radical pathway for direct C-X cleavage, sigma-bond metathesis of the ortho-C-H bond Of eta(1)-coordinated C6H5X, and beta-halogen elimination from base-free compound 3X.