[Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH3)2] | 863221-62-9

• 英文名称: [Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH3)2]
• 英文别名: [Ti(N-t-Bu)(1,4,7-trimethyl triazacyclononane)Me2]；Ti(N(t)Bu)(1,4,7-trimethyltriazacyclononane)Me2；[Ti(N-t-Bu)(Me3[9]aneN3)Me2]；Ti(N(t)Bu)(Me3[9]aneN3)Me2；Ti(Nt-Bu)(Me3[9]aneN3)Me2；Ti(NtBu)(Me3[9]aneN3)Me2
• CAS: 863221-62-9
• 化学式: C₁₅H₃₆N₄Ti
• 分子量: 320.358
• InChiKey: IFSGIBXAYYTBBR-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)(CH3)2] 、 三苯碳四(五氟苯基)硼酸盐 以 further solvent(s) 为溶剂， 生成 [TiMe(Nt-Bu)(Me3[9]aneN3)][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) 、 甲基锂 以 四氢呋喃 、 乙醚 为溶剂， 以70%的产率得到[Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH3)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

• Imido Titanium Ethylene Polymerization Catalysts Containing Triazacyclic Ligands
  作者：Nico Adams、Henricus J. Arts、Paul D. Bolton、Dan Cowell、Stuart R. Dubberley、Nic. Friederichs、Craig M. Grant、Mirko Kranenburg、Andrew J. Sealey、Bing Wang、Paul J. Wilson、Martin Zuideveld、Alexander J. Blake、Martin Schröder、Philip Mountford

  DOI：10.1021/om0603316

  日期：2006.7.1

  of 1 and 6 (linked by either the macrocycle or imido ligand to a 1% cross-linked polystyrene support) and representative Me3[6]aneN3 solution phase systems Ti(NR)(R3[6]aneN3)Cl2 (R = Me or n-dodecyl) were also synthesized. At ambient temperature, solution phase Me3[9]aneN3 catalyst systems were more active for ethylene polymerization (methyl aluminoxane (MAO) cocatalyst) than their solid phase-supported

  描述了由三氮杂环配体Me 3 [9] aneN 3和R 3 [6] aneN 3负载的衍生自亚氨基钛化合物的各种乙烯均聚催化剂的合成，性质和评估的全面说明（Me 3 [ 9] aneN 3＝ 1,4,7-三甲基三氮杂环壬烷； R 3 [6] aneN 3＝ 1,3,5-三甲基-或1,3,5-三（正十二烷基）三氮杂环己烷）。常规制备规模的反应提供了三氮杂环负载的亚氨基钛化合物Ti（NR）（Me 3 [9] aneN 3）Cl 2（R = t Bu（1），2,6--C 6 H ^ 3我2，2,6--C 6 H ^ 3我镨2中，Ph，C 6 ˚F 5，或CH 2 Ph（上6））。固相支持的1和6类似物（通过大环或亚氨基配体连接到1％交联的聚苯乙烯载体上）和代表性的Me 3 [6] aneN 3溶液相体系Ti（NR）（R 3 [6]还合成了aneN 3）Cl 2（R ＝ Me或正十二烷基）。在环境温度下，固溶相为Me3
• AlMe₃ and ZnMe₂ Adducts of a Titanium Imido Methyl Cation:  A Combined Crystallographic, Spectroscopic, and DFT Study
  作者：Paul D. Bolton、Eric Clot、Andrew R. Cowley、Philip Mountford

  DOI：10.1021/ja065638a

  日期：2006.11.1

  transition metal alkyl cation. At room temperature, all three metal-bound methyls of 8+ underwent rapid exchange with those of free ZnMe2, whereas at 233 K only the terminal Zn-Me group exchanged significantly. Addition of AlMe3 to 8+ quantitatively formed 7+ and ZnMe2. Reaction of 4+ with Cp2ZrMe2 gave [Ti(NtBu)Me2(mu-CH2)[9]aneN3}(mu-CH2)ZrCp2]+ (10+) via a highly selective double C-H bond activation

  描述了钛亚氨基甲基阳离子 [Ti(NtBu)(Me3[9]aneN3)Me]+ (4+) 与 AlMe3 和 ZnMe2 反应的联合实验和 DFT 研究。4+ 与 AlMe3 的反应得到 [Ti(NtBu)(Me3[9]aneN3)(mu-Me)2AlMe2]+ (7+)，这是第一个结构表征的过渡金属烷基阳离子的 AlMe3 加合物和假定的模型MAO 活化的烯烃聚合中的静止状态。4+ 与 ZnMe2 的反应也得到了一个甲基桥连的异双核物质，即 [Ti(mu-NtBu)(Me3[9]aneN3)(mu-Me)2ZnMe]+ (8+)，这是第一个直接观察到的 ZnMe2 加合物过渡金属烷基阳离子。在室温下，8+ 的所有三种金属结合甲基都与游离 ZnMe2 的甲基进行了快速交换，而在 233 K 时，只有末端 Zn-Me 基团发生了显着的交换。将 AlMe3 添加到 8+ 定量地形成了 7+ 和
• 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.