[(η5-C5Me5)TiMe2(NP(C(CH3)3)3)] | 532434-89-2

• 英文名称: [(η5-C5Me5)TiMe2(NP(C(CH3)3)3)]
• 英文别名: Cp(*)((t)Bu3P=N)Ti(CH3)2；Cp*(t-Bu3P=N)TiMe2
• CAS: 532434-89-2
• 化学式: C₂₄H₄₈NPTi
• 分子量: 429.506
• InChiKey: REKHWFLIGPKNOK-UHFFFAOYSA-N

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)TiMe2(NP(C(CH3)3)3)] 在 三苯碳四(五氟苯基)硼酸盐 作用下， 生成
  参考文献：
  名称：

  甲苯和α-烯烃作为自由基清除剂：导致苄基和“休眠”钛烯丙基络合物的均相链转移机理的直接NMR证据

  摘要：

  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。

  DOI：

  10.1021/acs.organomet.8b00755
• 作为产物：
  描述：

  [(η5-C5Me5)TiCl2(NP((CH3)3C)3)] 、 甲基氯化镁 以 乙醚 为溶剂， 反应 16.0h， 生成 [(η5-C5Me5)TiMe2(NP(C(CH3)3)3)]
  参考文献：
  名称：

  甲苯和α-烯烃作为自由基清除剂：导致苄基和“休眠”钛烯丙基络合物的均相链转移机理的直接NMR证据

  摘要：

  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。

  DOI：

  10.1021/acs.organomet.8b00755

文献信息

• An Approach to Catalyst Design:  Cyclopentadienyl-Titanium Phosphinimide Complexes in Ethylene Polymerization
  作者：Douglas W. Stephan、Jeffrey C. Stewart、Frédéric Guérin、Silke Courtenay、James Kickham、Emily Hollink、Chad Beddie、Aaron Hoskin、Todd Graham、Pingrong Wei、Rupert E. v. H. Spence、Wei Xu、Linda Koch、Xiaoliang Gao、Daryll G. Harrison

  DOI：10.1021/om020954t

  日期：2003.4.1

  for polymerization catalyst design has been developed based on the steric and electronic analogy of bulky phosphinimides to cyclopentadienyl ligands. To this end, the family of complexes of the form (Cp†)TiCl2(NPR3) has been prepared and characterized. Alkyl and aryl derivatives of these species have also been synthesized, and a number have been evaluated for use as catalyst precursors in olefin polymerization

  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。
• A new weakly coordinating aluminate anion incorporating a chelating perfluoro-bis-anilido ligand
  作者：Joshua C. Smith、Kuangbiao Ma、Warren E. Piers、Masood Parvez、Robert McDonald

  DOI：10.1039/c0dt00846j

  日期：——

  The synthesis of the fully fluorinated bis-anilido ligand N,N′-bis-pentafluorophenyl-3,4,5,6-tetrafluorophenylene-1,2-diamine, 1 is described. Reaction of one or two equivalents of 1 with AlMe3 gives aluminium compounds incorporating one or two ligands, the latter being the protonated form of a new weakly coordinating anion (WCA), 3-H. Alternatively, reaction of 1 with LiAlH4 yields the lithium salt of this anion, 3-Li, which may be employed as a reagent for preparing the trityl and N,N-dimethylanilinium salts of the aluminate anion. All ion pairs are fully characterized and the use of 3-Ph3C to generate titanium-based alkyl cations is also described.

  本文介绍了全氟双苯胺配体 N,N′-双五氟苯基-3,4,5,6-四氟苯-1,2-二胺 1 的合成。将一个或两个当量的 1 与 AlMe3 反应，可得到含有一个或两个配位体的铝化合物，后者是新的弱配位阴离子（WCA）3-H 的质子化形式。或者，将 1 与 LiAlH4 反应，可得到该阴离子的锂盐 3-Li，该锂盐可用作制备铝酸盐阴离子的三苯甲基和 N,N-二甲基苯胺盐的试剂。对所有离子对进行了全面描述，并介绍了使用 3-Ph3C 生成钛基烷基阳离子的方法。
• Selective Catalytic Dimerization of Neohexene by [Cp*Ti(NP^tBu₃)Me][B(C₆F₅)₄]
  作者：Dawn M. Friesen、Warren E. Piers、Masood Parvez

  DOI：10.1021/om800790d

  日期：2008.12.22

  The known titanium alkyl cation [Cp*Ti(NPtBu3)Me][B(C6F5)4], supported by a bulky phosphinimide donor, was found to react with 3 equiv of 3,3-dimethyl-1-butene (neohexene) to generate another alkyl cation in which the alkyl group is derived from two dimerized equivalents of the substrate olefin. This species, 1, was characterized in detail by spectroscopic methods and via X-ray crystallographic determinations

  发现由庞大的次膦酰亚胺供体支撑的已知钛烷基阳离子[Cp * Ti（NP t Bu 3）Me] [B（C 6 F 5）4 ]与3当量的3,3-二甲基-1反应-丁烯（新己烯）生成另一个烷基阳离子，其中烷基衍生自底物烯烃的两个二聚当量。本种，1通过光谱方法和通过X射线的2及其衍生物的晶体学测定，其特点详细地，THF加合物（2）和所述中性氯化物衍生物3形成在加入的Cl -至1。详细的机械实验建议1通过将新己烯插入[Cp * Ti（NP t Bu 3）Me] [B（C 6 F 5）4 ]的Ti-Me键中，可得到可检测的中间体（4），并对其进行了光谱表征。阳离子4在σ键复分解反应中与烯烃C H键反式反应至另一当量新己烯的叔丁基基团，形成未检测到的阳离子乙烯基中间体，该中间体迅速插入第三当量新己烯以生成1。氘标记的研究与此机理相吻合。化合物1是新己烯二聚反应的催化循环的静止状态；在催化条件下（95°C，[新己烯]
• 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.