tris((5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl)methyl)amine | 955934-86-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: tris((5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl)methyl)amine
• 英文别名: tris-(5-mesityl-1H-pyrrol-2-ylmethyl)-amine；tris(5-mesitylpyrrol-2-ylmethyl)amine；H3tpaMes；N(CH2C4H3N(2,4,6-C6H2Me3))3；N(CH2C4H3NMes)3；1-[5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl]-N,N-bis[[5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl]methyl]methanamine
• CAS: 955934-86-8
• 化学式: C₄₂H₄₈N₄
• 分子量: 608.87
• InChiKey: SNQWCIHOOPIVFT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  46
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  50.6
• 氢给体数：
  3
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tris((5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl)methyl)amine 、 tetrachlorobis(tetrahydrofurano)molybdenum(IV) 在 LiN(Si(CH₃)3)2 作用下， 以 四氢呋喃 为溶剂， 以0%的产率得到MoCl(N(CH2C4H2N(2,4,6-C6H2Me3))3)
  参考文献：
  名称：

  Tris(pyrrolyl-α-methyl)amines that Sterically Protect a Trigonal Metal Site

  摘要：

  Three substituted tris(pyrrolyl-alpha-methyl)amines (H-3[Aryl(3)TPA]) (Aryl = 2,4,6-C6H2Me3, 2,4,6-C6H2(i7Pr)(3) (Trip), or 3,5-C6H3(CF3)(2)) have been prepared. An X-ray study of [TriP(3)TPA]MoCl shows it to be a distorted trigonal bipyramidal species in which the 2,4,6-triisopropylphenyl substituents surround and protect the apical chloride. Attempts to prepare other Mo, Zr, and Hf complexes yielded species in which one pyrrole-containing arm remained free (Mo) or dimethylamine remained in the coordination sphere of [Aryl(3)TPA](3-) complexes (Zr, Hf).

  DOI：

  10.1021/ic701472y
• 作为产物：
  描述：

  聚合甲醛 、 2-mesitylpyrrole 在 氯化铵 作用下， 以 水 为溶剂， 生成 tris((5-(2,4,6-trimethylphenyl)-1H-pyrrol-2-yl)methyl)amine
  参考文献：
  名称：

  三角锥铁（II）吡咯烷配合物家族中的慢磁弛豫

  摘要：

  我们提出了一系列由通式 [M(solv)(n)][(tpa(R))Fe] (M = Na , R = 叔丁基 (1), 苯基 (4); M = K, R = 甲基 (2), 2,4,6-三异丙基苯基 (3), 2,6-二氟苯基 (5)) 及其表征X 射线晶体学、穆斯堡尔光谱和高场 EPR 光谱。在最近报道的甲基衍生物 2 中发现慢磁弛豫的基础上进行扩展，这种同源系列的高自旋铁 (II) 配合物能够初步探索配体场如何影响静态和动态磁行为。磁化实验揭示了大的单轴零场分裂参数 D = -48、-44、-30、-26 和 -6.2 cm(-1) 分别为 1-5，证明轴向磁各向异性的强度随着铁（II）中心配体场强度的增加而变化。在 2,6-二氟苯基取代 5 的情况下，高场 EPR 实验提供了零场分裂参数 (D = -4.397(9) cm(-1)) 的独立确定，与获得的参数合理一致从拟合到磁化数据。交流磁化率测量表明

  DOI：

  10.1021/ja105291x

文献信息

• Slow Magnetic Relaxation in a Family of Trigonal Pyramidal Iron(II) Pyrrolide Complexes
  作者：W. Hill Harman、T. David Harris、Danna E. Freedman、Henry Fong、Alicia Chang、Jeffrey D. Rinehart、Andrew Ozarowski、Moulay T. Sougrati、Fernande Grandjean、Gary J. Long、Jeffrey R. Long、Christopher J. Chang

  DOI：10.1021/ja105291x

  日期：2010.12.29

  agreement with that obtained from fits to magnetization data. Ac magnetic susceptibility measurements indicate field-dependent, thermally activated spin reversal barriers in complexes 1, 2, and 4 of U(eff) = 65, 42, and 25 cm(-1), respectively, with the barrier of 1 constituting the highest relaxation barrier yet observed for a mononuclear transition metal complex. In addition, in the case of 1, the large range

  我们提出了一系列由通式 [M(solv)(n)][(tpa(R))Fe] (M = Na , R = 叔丁基 (1), 苯基 (4); M = K, R = 甲基 (2), 2,4,6-三异丙基苯基 (3), 2,6-二氟苯基 (5)) 及其表征X 射线晶体学、穆斯堡尔光谱和高场 EPR 光谱。在最近报道的甲基衍生物 2 中发现慢磁弛豫的基础上进行扩展，这种同源系列的高自旋铁 (II) 配合物能够初步探索配体场如何影响静态和动态磁行为。磁化实验揭示了大的单轴零场分裂参数 D = -48、-44、-30、-26 和 -6.2 cm(-1) 分别为 1-5，证明轴向磁各向异性的强度随着铁（II）中心配体场强度的增加而变化。在 2,6-二氟苯基取代 5 的情况下，高场 EPR 实验提供了零场分裂参数 (D = -4.397(9) cm(-1)) 的独立确定，与获得的参数合理一致从拟合到磁化数据。交流磁化率测量表明
• N₂O Activation and Oxidation Reactivity from a Non-Heme Iron Pyrrole Platform
  作者：W. Hill Harman、Christopher J. Chang

  DOI：10.1021/ja076842g

  日期：2007.12.1

  of activating N2O, an appealing yet challenging oxidant, for oxygen atom transfer. The first generation tpaPhFe complex reacts with oxygen atom donors to generate a ligand hydroxylated species by intramolecular C−H activation and oxygenation. The second-generation tpaMesFe system expands on this reactivity to intermolecular hydrogen atom abstraction chemistry through N2O activation. The observation

  我们报告了一个新的非血红素铁吡咯配合物家族的设计、合成和氧化反应性。最具反应性的同系物能够激活 N2O，这是一种有吸引力但具有挑战性的氧化剂，用于氧原子转移。第一代 tpaPhFe 复合物与氧原子供体反应，通过分子内 C−H 活化和氧化生成配体羟基化物质。第二代 tpaMesFe 系统通过 N2O 活化将这种反应性扩展到分子间氢原子提取化学。对芳烃 CH 羟基化和外部氢原子供体的消耗的观察表明，沿着这些反应途径存在一种以金属为中心的强氧化剂，可能是铁 (IV)-氧代物种。这项工作为高价铁反应性建立了一个新的协调平台。
• A Structurally Characterized Nitrous Oxide Complex of Vanadium
  作者：Nicholas A. Piro、Michael F. Lichterman、W. Hill Harman、Christopher J. Chang

  DOI：10.1021/ja110798w

  日期：2011.2.23

  Nitrous oxide (N2O), a widespread greenhouse gas, is a thermodynamically potent and environmentally green oxidant that is an attractive target for activation by metal centers. However, N2O remains underutilized owing to its high kinetic stability, and the poor ligand properties of this molecule have made well-characterized metal-N2O complexes a rarity. We now report a vanadium-pyrrolide system that reversibly binds N2O at room temperature and provide the first single-crystal X-ray structure of such a complex. Further characterization by vibrational spectroscopy and DFT calculations strongly favor assignment as a linear, N-bound metal-N2O complex.
• Tris(pyrrolyl-α-methyl)amines that Sterically Protect a Trigonal Metal Site
  作者：Keith M. Wampler、Richard R. Schrock

  DOI：10.1021/ic701472y

  日期：2007.10.1

  Three substituted tris(pyrrolyl-alpha-methyl)amines (H-3[Aryl(3)TPA]) (Aryl = 2,4,6-C6H2Me3, 2,4,6-C6H2(i7Pr)(3) (Trip), or 3,5-C6H3(CF3)(2)) have been prepared. An X-ray study of [TriP(3)TPA]MoCl shows it to be a distorted trigonal bipyramidal species in which the 2,4,6-triisopropylphenyl substituents surround and protect the apical chloride. Attempts to prepare other Mo, Zr, and Hf complexes yielded species in which one pyrrole-containing arm remained free (Mo) or dimethylamine remained in the coordination sphere of [Aryl(3)TPA](3-) complexes (Zr, Hf).
• Synthesis and structural characterization of a trispyrrole iron(II) complex K(dme)4[tpaMesFe] and application in nitrous oxide dependent coupling reactions
  作者：Maik Weidauer、Elisabeth Irran、Stephan Enthaler

  DOI：10.1016/j.inoche.2015.01.028

  日期：2015.4

  A new synthetic route to the trispyrrole iron(II) complex K(dme)(4)[tpa(Mes)Fe]} was established starting from BOC-protected pyrrol via synthesis of the corresponding boronic acid, cross-coupling reaction, deprotection, triple Mannich reaction, a deprotonation and finally a salt metathesis. The complex was characterized and applied in iron-catalyzed coupling reactions. In more detail, with catalytic amounts of K(dme)(4)[tpa(Mes)Fe] the homo-coupling of aromatic Grignard reagents as well as the hetero-coupling of aromatic Grignard reagents were feasible. Noteworthy, to force the reaction nitrous oxide was added to realize yields up to 93% at mild reaction conditions. (C) 2015 Elsevier B.V. All rights reserved.