(η5-cyclopentadienyl)Ti(NP(t-Bu)3)Cl2 | 219792-35-5

• 英文名称: (η5-cyclopentadienyl)Ti(NP(t-Bu)3)Cl2
• 英文别名: [(η5-C5H5)TiCl2NP(t-Bu3)]；[CpTiCl2(NP(C(CH3)3)3)]
• CAS: 219792-35-5
• 化学式: C₁₇H₃₂Cl₂NPTi
• 分子量: 400.208
• InChiKey: RTJMTALGOUKFPN-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-cyclopentadienyl)Ti(NP(t-Bu)3)Cl2 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：

  三氯一茂钛 、 N-Trimethylsilyl-tri(tert.-butyl)phosphinimin 以 苯 为溶剂， 以92%的产率得到(η5-cyclopentadienyl)Ti(NP(t-Bu)3)Cl2
  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

• 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
• Group IV phosphinimide amide complexes
  作者：Emily Hollink、Pingrong Wei、Douglas W Stephan

  DOI：10.1139/v04-141

  日期：2004.11.1

  Complexes of formula TiCp(NPR₃)(NMe₂)₂ (R = t-Bu 1, Ph 2) were prepared via salt metathesis of TiCp(NPR₃)Cl₂ with a slight excess of LiNMe₂. The species Ti(NP-t-Bu₃)(NMe₂)₃ (3) was obtained as a by-product. The related derivative ZrCp(NP-t-Bu₃)(NMe₂)₂ (4) was also prepared. Reaction of TiCp(NP-t-Bu₃)Cl₂ with LiNHC₆H₃(2,6-i-Pr₂) afforded TiCp(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))Cl (5) and Ti(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))₃ (6). In a similar manner, the Zr analogs ZrCp(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))Me (7) and ZrCp(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))₂ (8) were also prepared. X-ray structural data for compounds 5, 6, and 8 are reported. Reactivity of these phosphinimide–amide derivatives was explored. While these species do not yield imide derivatives upon thermolysis, reaction of 5 with excess AlMe₃ afforded TiCp(NP-t-Bu₃)Me₂ while reaction with 1 equiv. of AlMe₃ gave TiCp(NP-t-Bu₃)MeCl (9) and Al₂(m-NHC₆H₃(2,6-i-Pr₂))₂Me₄ (10). Key words: titanium, zirconium, phosphinimide, amide, ligand metathesis.

  以TiCp(NPR₃)Cl₂为前驱体，通过与略微过量的LiNMe₂盐交换反应制备了式为TiCp(NPR₃)(NMe₂)₂ (R = t-Bu 1, Ph 2)的配合物。副产物Ti(NP-t-Bu₃)(NMe₂)₃ (3)也被得到。相关的衍生物ZrCp(NP-t-Bu₃)(NMe₂)₂ (4)也被制备。将TiCp(NP-t-Bu₃)Cl₂与LiNHC₆H₃(2,6-i-Pr₂)反应得到了TiCp(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))Cl (5)和Ti(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))₃ (6)。类似地，Zr类似物ZrCp(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))Me (7)和ZrCp(NP-t-Bu₃)(NHC₆H₃(2,6-i-Pr₂))₂ (8)也被制备。报道了化合物5、6和8的X射线结构数据。探索了这些膦亚胺-酰胺衍生物的反应性。虽然这些物种不会在热解过程中产生酰亚胺衍生物，但是5与过量的AlMe₃反应产生了TiCp(NP-t-Bu₃)Me₂，而与1当量的AlMe₃反应则产生了TiCp(NP-t-Bu₃)MeCl (9)和Al₂(m-NHC₆H₃(2,6-i-Pr₂))₂Me₄ (10)。关键词：钛，锆，膦亚胺，酰胺，配体交换。
• Phosphinimides as a Steric Equivalent to Cyclopentadienyl:  An Approach to Ethylene Polymerization Catalyst Design
  作者：Douglas W. Stephan、Jeffrey C. Stewart、Frédéric Guérin、Rupert E. v. H. Spence、Wei Xu、Daryll G. Harrison

  DOI：10.1021/om980955e

  日期：1999.3.1

  Complexes of the form (Cp dagger)TiCl2(NPR3) and the analogous dimethyl derivatives (Cp dagger)TiMe2(NPR3) have been prepared. These species in the presence of MAO, B(C6F5)(3), or [Ph3C][B(C6F5)(4)] are active catalysts for ethylene polymerization.
• η¹- and η⁵-Indenyl and Cyclopentadienyl Tri<i>-tert</i>-Butylphosphoraneiminatotitanium Complexes
  作者：Frédéric Guérin、Chad L. Beddie、Douglas W. Stephan、Rupert E. v. H. Spence、Ryan Wurz

  DOI：10.1021/om010298h

  日期：2001.8.1

  The compounds (indenyl)Ti(NP-t-Bu-3)Cl-2 (4), Cp2Ti(NP-t-Bu-3)Cl (6), (indenyl)(2)Ti(NP-t-Bu-3)-Cl (7), Cp(indenyl)Ti(NP-t-Bu-3)Cl (8), Cp3Ti(NP-t-Bu-3) (9), (indenyl)(3)Ti(NP-t-Bu-3) (10), and Cp(indenyl)(2)Ti(NP-t-Bu-3) (11) are readily derived from reaction with (dme)NaCp or Li-(indenyl) with CpTi(NP-t-Bu-3)Cl-2 (1) or 4 in the appropriate stoichiometry. X-ray crystallograpby studies of (indenyl)Ti(NP-t-Bu-3)Me-2 (5) and 7-11 are reported. In the case of 6 and 9 two cyclopentadienyl rings are bound to the metal in a eta (5)-bonding mode, whereas in 7, 8, 10, and 11 one of the cyclopentadienyl or indenyl ligands is bound in an eta (5) mode and the remainder in an eta (1)-fashion. In the case of 10, temperature-dependent H-1 NMR spectra infer a eta (5)-eta (1) ligand exchange process with an approximate barrier of 8-9 kcal/mol. Steric crowding appears to be the major factor determining the binding modes of the cyclopentadienyl and indenyl ligands. These structural data result in a view of the phosphoraneiminato ligand as a sterically demanding, four-electron donor ligand.
• Synthesis, Structure, and Single-Crystal EPR Study of [Cp(<i>t-</i>Bu₃PN)Ti(μ-Cl)]₂
  作者：Raymond C. W. Sung、Silke Courtenay、Bruce R. McGarvey、Douglas W. Stephan

  DOI：10.1021/ic991305l

  日期：2000.6.1

  The reduction of CpTi(NPt-Bu-3)Cl-2 with Mg powder in benzene proceeds slowly to give [CpTi(NPt-Bu-3(mu-Cl)](2))12 tli. An X-ray crystallographic study confirmed 1 is a centrosymmetric chloro-bridged dimer in the solid state. A single-crystal EPR study of 1 permitted the determination of the best-fitted values for the diagonal spin Hamiltonian parameters. This appears to be the first EPR single-crystal study of a Ti(III)-Ti(III) dimer. The implications of these data are considered and discussed in light of extended Huckel molecular orbital calculations.