[Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH2Si(CH3)3)2] | 863221-63-0

• 英文名称: [Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH2Si(CH3)3)2]
• 英文别名: [Ti(trimethylsilylmethyl)2(tert-butylimido)(1,4,7-trimethyltriazacyclononane)]
• CAS: 863221-63-0
• 化学式: C₂₁H₅₂N₄Si₂Ti
• 分子量: 464.722
• InChiKey: KEWULVILEDOHJK-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：

  [Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH2Si(CH3)3)2] 、 三苯碳四(五氟苯基)硼酸盐 以 not given 为溶剂， 生成 [Ti(Nt-Bu)(Me3[9]aneN3)(CH2SiMe3)][B(C6F5)4]
  参考文献：
  名称：

  Discovery and evaluation of highly active imidotitanium ethylene polymerisation catalysts using high throughput catalyst screening

  摘要：

  采用半自动化程序制备了约 50 种咪唑钛前催化剂[Ti(NR)(Me3[9]aneN3)Cl2]（R = 烷基或芳基；Me3[9]aneN3 = 1,4,7-三甲基三氮杂环壬烷），产率良好。3 400 至 10 000 kg(PE) mol-1 h-1 bar-1。

  DOI：

  10.1039/b313921b
• 作为产物：
  描述：

  TiCl2(t-BuN)(1,3,5-trimethyl-1,3,5-triazacyclononane) 、 trimethylsilylmethyllithium 以 苯 为溶剂， 以72%的产率得到[Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH2Si(CH3)3)2]
  参考文献：
  名称：

  茂金属样亚胺基钛二烷基钛化合物的合成，乙烯聚合能力及其与Al i Bu 3的反应

  摘要：

  一系列烷基和芳基亚氨基钛二烷基化合物Ti（N t Bu）（Me 3 [9] aneN 3）R 2（R = Me（1），CH 2 SiMe 3（3），CH 2 t Bu（4），CH 2 Ph（5）），Ti（NR）（Me 3 [9] aneN 3）Me 2（R = i Pr（6），Ph（7），3,5-C 6 H 3（CF 3）2（8），2,6-碳6 H3 i Pr 2（9），2-C 6 H 4 CF 3（10），2-C 6 H 4 t Bu（11））和Ti（NR）（Me 3 [9] aneN 3）（CH 2森达3）2（R =我PR（12）中，Ar ˚F（13））中制备和结晶学特征的情况下1，6 - 9，和11（ME 3 [9] ANEN3 = 1,4,7-三甲基三氮杂环壬烷; Ar F＝ C 6 F 5）。这些化合物中，等瓣与所述二茂钛的Cp 2 TIR 2，是在升高的温度下，除了热稳定的4。的反应7与[PH

  DOI：

  10.1021/om0606136

文献信息

• Experimental and DFT Studies of Cationic Imido Titanium Alkyls:  Agostic Interactions and C−H Bond and Solvent Activation Reactions of Isolobal Analogues of Group 4 Metallocenium Cations
  作者：Paul D. Bolton、Eric Clot、Nico Adams、Stuart R. Dubberley、Andrew R. Cowley、Philip Mountford

  DOI：10.1021/om060096r

  日期：2006.5.1

  Attempts to generate 7+ by reaction of 2 with [PhNMe2H][BArF4] in CH2Cl2 led to Ti(NtBu)(Me3[9]aneN3)Cl2 and [PhNMe2(CH2Cl)][BArF4] (12-BArF4) via a series of solvent activation reactions, the details of which have been elucidated. Reaction of 6+ or 7+ with Ph3PO afforded the adducts [Ti(NtBu)(Me3[9]aneN3)R(Ph3PO)]+, whereas with pyridine a C−H bond activation reaction occurred to give [Ti(NtBu)(

  Ti（N t Bu）（Me 3 [9] aneN 3）R 2（R = Me（1）或CH 2 SiMe 3（2））衍生的大环负载的亚氨基钛烷基钛阳离子的合成，反应和DFT研究描述了（Me 3 [9] aneN 3＝ 1,4,7-三甲基三氮杂环壬烷）。的反应1与1个当量的[PH 3 C] [巴˚F 4 ]或BAR ˚F 3（AR ˚F = C 6 ˚F 5中C）6 d 5Br提供了甲基阳离子[Ti（N t Bu）（Me 3 [9] aneN 3）Me] +（6 +），而当量为[Ph 3 C] [BARhref=https://www.molaid.com/MS_77868 target="_blank">BAr F 4 ]的一半时，通量甲基桥连形成同核双阳离子[Ti 2（N t Bu）2（Me 3 [9] aneN 3）2 Me 2（μ-Me）] +（10 +）。的反应1与[PH 3 C] [巴˚F 4 ]在CD 2氯2形成单氯化物阳离子[Ti（N t Bu）（Me 3 [9] aneN 3）Cl] +（8
• Well-defined imidotitanium alkyl cations: agostic interactions, migratory insertion vs.[2+2] cycloaddition, and the first structurally authenticated AlMe3 adduct of any transition metal alkyl cation
  作者：Paul D. Bolton、Eric Clot、Andrew R. Cowley、Philip Mountford

  DOI：10.1039/b504567c

  日期：——

  alkyl cations [Ti(NtBu)(Me3[9]aneN3)R]+ (R = Me (3+) or CH2SiMe3(4+)) possess either a very weak alpha-agostic or beta-Si-C agostic interactions, respectively, according to 13C and 29Si NMR and DFT studies; reaction of (4+) with iPrNCNiPr gives totally selective insertion into the Ti-alkyl bond; reaction of 3+ with AlMe3 gives the first structurally characterised AlMe3 adduct of a transition metal alkyl

  亚胺基钛烷基阳离子[Ti（NtBu）（Me3 [9] aneN3）R] +（R = Me（3+）或CH2SiMe3（4+））具有很弱的α-原子或β-Si-C原子间的弱相互作用。分别根据13C和29Si NMR和DFT研究；（4+）与iPrNCNiPr的反应完全选择性地插入到Ti-烷基键中; 3+与AlMe3的反应生成了过渡金属烷基阳离子的第一个结构表征的AlMe3加合物（Me3 [9] aneN3 = 1,4,7-三甲基三氮杂环壬烷）。
• Ti═NR vs Ti−R′ Functional Group Selectivity in Titanium Imido Alkyl Cations from an Experimental Perspective
  作者：Paul D. Bolton、Marta Feliz、Andrew R. Cowley、Eric Clot、Philip Mountford

  DOI：10.1021/om800709f

  日期：2008.12.8

  A study of the reactions of the titanium imido methyl cation [Ti((NBu)-Bu-t)(Me-3[9]aneN(3))X](+) (5(+), X = Me) and key analogues (6(+), X = CH2SiMe3; 7(+), X = Cl) with a range of unsaturated substrates provides a comprehensive evaluation of reaction site selectivity in transition-metal cations which contain both Ti=NR and Ti-R ' functional groups as potential sites for 2 pi + 2 pi cycloaddition and migratory insertion, respectively. Cations 5+ and 6(+) reacted with MeCN to form Ti-R ' insertion products. Insertion reactions were also exclusively observed in their reactions with N,N '-disubstituted carbodiimides or tert-butyl isocyanate. In contrast, reaction of the chloride cation 7+ with diisopropylcarbodiimide or tert-butyl isocyanate afforded the unusual a adducts [Ti((NBu)-Bu-t)(Me-3[9]aneN(3))(L)Cl](+) (L = (PrNCNi)-Pr-i Pr, (BuNCO)-Bu-t), which slowly underwent 2,7 + 2 pi cycloaddition. Reaction of 5+ with the internal alkynes PhCCR (R = Ph, SiMe3) also showed exclusive preference for insertion into the Ti-Me bond. In contrast, reaction with terminal alkynes RCCH (R = Ph, SiMe3) yielded only the azametallacyclic products via 2-pi + 2 pi cycloaddition reactions. The chloride cation 7+ also underwent a 2 pi + 2 pi cycloaddition with PhCCH but was unreactive toward PhCCPh, ethylene, styrene, or 1-hexene.