2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene) | 1085283-29-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene)
• CAS: 1085283-29-9
• 化学式: C₄₀H₅₄N₄
• 分子量: 590.896
• InChiKey: WWBBCSVMTWLLDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.4
• 重原子数：
  44.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  48.78
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene) 、 三甲基铝 以 甲苯 为溶剂， 反应 16.0h， 以100%的产率得到
  参考文献：
  名称：

  双（β-二酮）配体双核铝配合物的合成与结构

  摘要：

  从三甲基铝与相应的双（β-二酮亚胺）反应中获得了一系列十个基于刚性，半刚性和柔性双（β-二酮）配体（NacNac）的双核烷基铝配合物。使用NMR和IR光谱以及元素分析对所有化合物进行了全面表征。通过单晶X射线衍射分析研究了五种化合物的分子结构。

  DOI：

  10.1002/zaac.201900193
• 作为产物：
  描述：

  对苯二胺 、 4-[(2,6-diisopropylphenyl)amino]pent-3-en-2-one 在 triethyloxonium fluoroborate 作用下， 生成 2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene)
  参考文献：
  名称：

  双（β-二酮）配体双核铝配合物的合成与结构

  摘要：

  从三甲基铝与相应的双（β-二酮亚胺）反应中获得了一系列十个基于刚性，半刚性和柔性双（β-二酮）配体（NacNac）的双核烷基铝配合物。使用NMR和IR光谱以及元素分析对所有化合物进行了全面表征。通过单晶X射线衍射分析研究了五种化合物的分子结构。

  DOI：

  10.1002/zaac.201900193

文献信息

• Synthesis of β-diketiminate-ligated bimetallic and monometallic lanthanide amide complexes and their reactivity with isoprene and AlMe3
  作者：Song Sun、Hao Ouyang、Yunjie Luo、Yong Zhang、Qi Shen、Yingming Yao

  DOI：10.1039/c3dt52014e

  日期：——

  The amine elimination of lanthanide tris(amide) complexes with the phenylene-bridged bis(β-diketiminate) ligands PARAMe-H2, METAMe-H2 and PARAPr-H2 (PARAMe-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene), METAMe-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(meta-phenylene), PARAPr-H2 = 2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(para-phenylene)), and the mono-β-diketiminate ligand L2,6-iPr2Ph-H (2,6-iPr2C6H3)NHC(Me)CHC(Me)N(C6H5)) afforded the bimetallic lanthanide amide complexes PARAMe-Ln[N(SiMe3)2]2}2 (Ln = Y (1), Sm (2)), METAMe-Y[N(SiMe3)2]2}2 (3), PARAPr-Ln[N(HSiMe2)2]2}2 (Ln = Y (4), Sm (5)), and the monomeric complexes L2,6-iPr2Ph-Y[N(SiMe3)2]2 (6) and L2,6-iPr2Ph-Y[N(HSiMe2)2]2 (7). In the presence of AlR3 and on activation with 1 equiv. of [Ph3C][B(C6F5)4], complexes 1–7 showed a high activity toward the 1,4-selective polymerization of isoprene. The heterometallic Y/Al methyl complex [L2,6-iPr2Ph]Y[(μ-Me)2AlMe2]2 (8) was prepared to elucidate the real active precursor in the polymerization.

  具有芳基桥接双(β-二酮亚胺)配体PARAMe-H2、METAMe-H2和PARAPr-H2的镧系金属三(酰胺)配合物的胺消除反应（PARAMe-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(对位苯)，METAMe-H2 = 2[2,6-Me2C6H3NHC(Me)C(H)C(Me)N]-(间位苯)，PARAPr-H2 = 2[2,6-iPr2C6H3NHC(Me)C(H)C(Me)N]-(对位苯)以及单β-二酮亚胺配体L2,6-iPr2Ph-H (2,6-iPr2C6H3)NHC(Me)CHC(Me)N(C6H5))，得到双金属镧系金属酰胺配合物PARAMe-Ln[N(SiMe3)2]2}2 (Ln = Y (1), Sm (2))、METAMe-Y[N(SiMe3)2]2}2 (3)、PARAPr-Ln[N(HSiMe2)2]2}2 (Ln = Y (4), Sm (5))，以及单体配合物L2,6-iPr2Ph-Y[N(SiMe3)2]2 (6)和L2,6-iPr2Ph-Y[N(HSiMe2)2]2 (7)。在AlR3存在的条件下，使用1当量[Ph3C][B(C6F5)4]激活后，复合物1–7表现出对异戊二烯1,4-选择性聚合的高活性。为阐明聚合中的真实活性前驱体，合成了异金属Y/Al甲基复合物[L2,6-iPr2Ph]Y[(μ-Me)2AlMe2]2 (8)。
• Dinuclear Aluminum Halide Complexes Based on Bis(β-diketiminate) Ligands: Synthesis, Structures, and Electrochemical Characterization
  作者：Marcella E. Desat、Robert Kretschmer

  DOI：10.1021/acs.inorgchem.9b02868

  日期：2019.12.2

  Twenty-three dinuclear aluminum halide complexes based on bis(β-diketiminate) ligands with various flexible and rigid bridging groups have been synthesized and fully characterized by NMR and IR spectroscopy, cyclic voltammetry, and elemental analysis. In addition, nine complexes were structurally characterized by means of single-crystal X-ray diffraction. Attempts to reduce the dinuclear species using

  合成了23种基于双（β-二酮）配体的双核卤化铝配合物，该配合物具有各种柔性和刚性桥联基团，并通过NMR和IR光谱，循环伏安法和元素分析对其进行了全面表征。另外，通过单晶X射线衍射在结构上表征了九种配合物。尝试使用C8K还原双核物种仍未成功，但循环伏安法研究的还原潜力表明了该原理的可行性。
• En Route to Bis-Carbene Analogues of the Heavier Group 13 Elements: Consideration of Bridging Group and Metal(I) Source
  作者：Marcella E. Desat、Robert Kretschmer

  DOI：10.1002/chem.201800925

  日期：2018.8.22

  (additional ligands, solvent molecules). In addition, the effect of the metal(I) precursor, and more specifically the counterion, on the synthetic access to bis‐carbene analogues of indium and thallium was investigated. For indium, only InI yields the desired dinuclear indium diyl. With InBr no reaction was observed, and using InCl gave rise to a mononuclear indium(III) compound. For thallium, both TlI

  为了探索通过连接支架对th的双卡宾类似物的金属-金属相互作用施加空间限制的影响，合成了七个具有一系列刚性，半刚性和柔性桥连支架的双核al二基。通过单晶XRD确定了其中四种化合物的固态分子结构，并将其与对所有物质进行的DFT计算结果进行了比较。这些化合物用作研究在不存在配位分子（附加配体，溶剂分子）的情况下金属与金属之间距离的模型。此外，还研究了金属（I）前体（更具体而言是抗衡离子）对铟和carb的双卡宾类似物合成途径的影响。对于铟 仅InI产生所需的二核铟二基。使用InBr，未观察到反应，并且使用InCl，产生单核铟（III）化合物。对于th，TlI和TlBr都允许使用相关的双卡宾类似物，尽管后者的收率要低得多。相反，未观察到与TlCl和TlBF的反应4。
• Well-Defined Molecular Magnesium Hydride Clusters: Relationship between Size and Hydrogen-Elimination Temperature
  作者：Julia Intemann、Jan Spielmann、Peter Sirsch、Sjoerd Harder

  DOI：10.1002/chem.201300684

  日期：2013.6.24

  between the cluster size and H2 release, the thermal decomposition of [NN‐(MgH)2}2] and two closely related systems that were based on similar ligands, that is, an octanuclear magnesium hydride cluster and a dimeric magnesium hydride species, have been investigated in detail. A lowering of the H2‐desorption temperature with decreasing cluster size is observed, in line with previously reported theoretical

  一种新的四核氢化镁簇，[ NN - （MGH）2 } 2 ]，它是基于A N  N-二耦合双-β-二亚胺基配体（NN 2- ），由的[反应得到NN ‐（Mg n Bu）2 } 2 ]与PhSiH 3。它的晶体结构显示出Mg原子和两组不同的氢化物离子几乎呈四面体排列，这在NMR光谱中引起了耦合（J = 8.5 Hz）。为了阐明团簇尺寸与H 2释放之间的关系，[ NN-（MgH）的热分解[2 } 2 ]以及基于相似配体的两个紧密相关的系统，即八核氢化镁簇和二聚氢化镁物种，已得到详细研究。观察到H 2解吸温度随团簇尺寸的减小而降低，这与先前报道的关于（MgH 2）n模型系统的理论预测相一致。氘标记研究进一步证明，释放出的H 2仅源自两个氢化物配体的氧化偶合，而不源自其他氢源，如β-二酮配体。[ NN ‐（MgH）2 } 2中DFT计算的电子密度的分析]其中说明了两个正式闭壳层h的违反直觉的相互作用-由3
• Bimetallic Calcium and Zinc Complexes with Bridged β-Diketiminate Ligands: Investigations on Epoxide/CO₂ Copolymerization
  作者：Dirk F.-J. Piesik、Sven Range、Sjoerd Harder

  DOI：10.1021/om800597f

  日期：2008.12.8

  A series of dinucleating bis(beta-diketiminate) ligands with rigid bridges has been prepared. In all cases the beta-diketiminate unit is 2,6-iPr(2)C(6)H(3)NC(Me)C(H)C(Me)N-(bridge), and the bridges are either paraphenylene, meta-phenylene or 2, 6-pyridylene (the dinucleating ligands are abbreviated as PARA-H-2,H- META-H-2 and PYR-H-2, respectively). These ligands have been converted to heteroleptic bimetallic calcium and zinc complexes. For calcium, only the PARA-phenylene bridged ligand led to a heteroleptic bimetallic calcium amide complex PARA-[CaN(SiMe3)(2) center dot THF](2). For the other ligands, homoleptic complexes have been isolated: META-Ca and PYR-Ca. For zinc, the whole range of heteroleptic amides could be isolated: PARA-[ZnN(SiMe3)(2)](2), META-[ZnN(SiMe3)(2)](2), and PYR-[ZnN(SiMe3)(2)](2). Analogue ethylzinc complexes have been prepared in quantitative yields: PARA-(ZnEt)(2), META-(ZnEt)(2), and PYR-(ZnEt)(2). Reactions of the ethylzinc complexes with SO2 gave access to the ethylsulfinate complexes META-(ZnO2SEt)(2) and PYR-(ZnO2SEt)(2); for the parci-phenylene bridged ligand no products could be isolated. Crystal structures of the following complexes are presented: (META-Ca)(2), PARA-[CaN(SiMe3)(2) center dot THF](2), PARA[ZnN(SiMe3)(2), META-[ZnN(SiMe3)(2)](2), PYR-(ZnEt)(2), and PYR-(ZnO2SEt)(2). All heteroleptic complexes have been tested for activity in the copolymerization of cyclohexene oxide (CHO) and CO,. The bimetallic complex PARA-[CaN(SiMe3)(2)-THF](2) is not active. For zinc, the PARA and META complexes were found to be active under highly concentrated conditions (Zn/CHO ratio of 1/1000; no solvent), but no significant polymer yields could be achieved with PYR complexes. This is either due to conformational changes of the complex or to coordination of the pyridylene N atom to the catalytic centers. The order of activity found in the bimetallic zinc complexes is META > PARA. This is likely due to a more advantageous Zri center dot center dot center dot Zn distance in the meta-phenylene bridged bimetallic catalysts. There are several indications for bimetallic action. First of all, the ethylzinc systems PARA-(ZnEt)(2) and META-(ZnEt)(2) initiate CHO/CO2 copolymerization, whereas monometallic ethylzinc catalysts are not reactive. Second, the bimetallic zinc catalysts are also highly active under diluted conditions: a low metal/CHO ratio of 1/3000 gave high-MW polyiners (M-n > 100.000, PDI = 1.33) with essentially only carbonate linkages. In contrast, monometallic systems show a drastic loss of activity upon dilution. Finally, the bimetallic catalyst META-[ZnN(SiMe3)212 shows a significantly higher activity than a comparable monometallic model system.