tris[(6-amino-2-pyridyl)methyl]amine | 401560-62-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: tris[(6-amino-2-pyridyl)methyl]amine
• 英文别名: tris(6-amino-2-pyridylmethyl)amine；TAPA；N(CH2Py-6-NH2)3；Tris(6-aminopyridine-2-ylmethyl)amine；6-[[bis[(6-aminopyridin-2-yl)methyl]amino]methyl]pyridin-2-amine
• CAS: 401560-62-1
• 化学式: C₁₈H₂₁N₇
• 分子量: 335.412
• InChiKey: DBPJVRYMTKLXIM-UHFFFAOYSA-N

物化性质

• 沸点：
  556.8±45.0 °C(Predicted)
• 密度：
  1.320±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  120
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  苯甲酰基异硫氰酸酯 、 tris[(6-amino-2-pyridyl)methyl]amine 以 乙醇 为溶剂， 反应 0.5h， 以37%的产率得到N-[[6-[[bis[[6-(benzoylcarbamothioylamino)pyridin-2-yl]methyl]amino]methyl]pyridin-2-yl]carbamothioyl]benzamide
  参考文献：
  名称：

  新型三硫脲三脚形配体的配位行为；一系列过渡金属配合物的结构变化†

  摘要：

  研究了三硫脲三（2-吡啶基甲基）胺配体（L 1）与一系列过渡金属离子的配位化学。晶体学数据表明，没有几何偏好的大金属离子，例如Mn（II）和Cd（II），将形成七个配位的单峰八面体络合物，而较小的金属离子，例如Zn（II）则支持五个配位的八面体。三角双锥体结构。Ni（II）络合物以与相关的双硫脲络合物相似的方式显示出对八面体几何形状的强烈偏好，从而导致配体不对称结合。报告了这些配合物的光谱（IR和NMR），光谱（MS）以及电化学数据。

  DOI：

  10.1039/c6dt01148a
• 作为产物：
  描述：

  tris(((6-pivaloylamido)-2-pyridyl)methyl)amine 在 盐酸 作用下， 反应 24.0h， 以71%的产率得到tris[(6-amino-2-pyridyl)methyl]amine
  参考文献：
  名称：

  Relative importance of hydrogen bonding and coordinating groups in modulating the zinc–water acidity

  摘要：

  锌 (II) 结合水分子附近存在第二球体 -NH2 基团，可将其酸度增强约 10%。 2 pKa 单位。

  DOI：

  10.1039/b310956a

文献信息

• Tristhiourea tripodal metal complexes
  申请人：Umm Al-Qura University

  公开号：US08552190B1

  公开（公告）日：2013-10-08

  The tristhiourea tripodal metal complexes are a group of coordination compounds having a transition metal linked by coordinate covalent bods to a chelating agent. The chelating agent has a tris-(6-amino-2-pyridylmethyl)amine (TAPA) backbone and three thiourea ligands bonded to the three legs of the TAPA backbone, respectively. The transition metal bonds to the amino groups of the TAPA backbone, and the thiourea ligands hydrogen bond to the anion guest remote from the transition metal. The chelating agent has a symmetrical C3v tripodal cavity that is selective for tetrahedral anions. The transition metal is selected from the group consisting of cadmium, manganese, cobalt, nickel, copper, and zinc. The tristhiourea tripodal metal complexes may be used in colorimetric sensors, selectively permeable membranes, filtration media for separating tetrahedral anions (such as phosphate and perchlorate) from mixtures, and similar applications.

  三硫脲三脚架金属配合物是一类配位化合物，其中过渡金属通过配位共价键与螯合剂相连。螯合剂具有三-(6-氨基-2-吡啶甲基)胺（TAPA）骨架，三个硫脲配体分别与TAPA骨架的三条腿结合。过渡金属与TAPA骨架的氨基结合，硫脲配体与远离过渡金属的阴离子客体形成氢键。螯合剂具有对四面体阴离子具有选择性的对称C3v三脚架空腔。过渡金属选自镉、锰、钴、镍、铜和锌。三硫脲三脚架金属配合物可用于比色传感器、选择性渗透膜、用于从混合物中分离四面体阴离子（如磷酸盐和高氯酸盐）的过滤介质等应用。
• Fixation of CO₂by Hydroxozinc(II) Complex with Pyridylamino Type Ligand
  作者：Syuhei Yamaguchi、Teppei Takahashi、Akira Wada、Yasuhiro Funahashi、Tomohiro Ozawa、Koichiro Jitsukawa、Hideki Masuda

  DOI：10.1246/cl.2007.842

  日期：2007.7.5

  Reaction of hydroxozinc(II) complex bearing amino group with CO2 gave carbamate product, whose generation and reaction mechanism have been studied structurally and spectroscopically as a structural/functional model of biotin-dependent carboxylase.

  含氨基的羟基锌（II）复合物与 CO2 反应生成氨基甲酸酯产物，作为生物素依赖性羧化酶的结构/功能模型，对其生成和反应机理进行了结构和光谱研究。
• The strength of hydrogen bonding to metal-bound ligands can contribute to changes in the redox behaviour of metal centres
  作者：Juan C. Mareque Rivas、Sarah L. Hinchley、Laurent Metteau、Simon Parsons

  DOI：10.1039/b516234c

  日期：——

  [(L(Piv-1,2,3))Cu(I)Cl] and [(L(Piv-1,2,3))Cu(II)Cl]+ complexes in acetonitrile show that the intramolecular N-H...Cl-Cu hydrogen bonding weakens in the order L(Piv-1) > L(Piv-2) > L(Piv-3), and that it is stronger in the Cu(I) complexes. The 1H NMR spectra of the [(L(Piv1,2,3))Cu(I)Cl] complexes are in complete agreement with the IR data, and reveal that the stability of the Cu(I) complexes to oxidation

  一系列基于三（吡啶基-2-甲基）胺TPA的九个三脚架四齿配体，在一个，两个和三个吡啶6位中具有氢键供体R（R = NH2氨基，L（Am-1,2， 3）; NHCH2（t）Bu新戊基氨基，L（Np-1,2,3）; NHCO（t）Bu pivaloylamido，L（Piv-1,2,3））和TPA用于研究不同氢的影响键合微环境对其LCuCl配合物的电化学性能的影响。氢键供体是刚性预组织的，并适合于分子内NH ... Cl-Cu氢键的取向。循环伏安法研究表明，作为配体的函数，Cu（II）/ Cu（I）对的还原电位遵循以下顺序：TPA L（Piv-2）> L（Piv-3）的顺序减弱，并且在Cu（I）配合物中更强。[（L（Piv1,2,3））Cu（I）Cl]配合物的1H NMR光谱与IR数据完全一致，并且揭示了Cu（I）配合物对空气中氧化的稳定性增加顺序为L（Piv-1）
• Complexes with Fe^III₂(μ-O)(μ-OH) Core Surrounded by Hydrogen-Bonding Interaction
  作者：Yasutaka Honda、Hidekazu Arii、Takeshi Okumura、Akira Wada、Yasuhiro Funahashi、Tomohiro Ozawa、Koichiro Jitsukawa、Hideki Masuda

  DOI：10.1246/bcsj.80.1288

  日期：2007.7.15

  Three new complexes with FeIII2(μ-O)(μ-OH) core surrounded with one, two, and three amino groups, that is, (6-amino-2-pyridylmethyl)bis(pyridylmethyl)amine (MAPA), bis(6-amino-2-pyridylmethyl)(pyridylmethyl)amine (BAPA), and tris(6-amino-2-pyridylmethyl)amine (TAPA), which act as hydrogen-bonding sites, were synthesized and characterized by electronic absorption spectroscopy and X-ray diffraction analysis. Their structural bond parameters, Fe–N(pyridine), Fe–N(amine), and Fe–μ-O(H) bonds, Fe···Fe distance, and Fe–O–Fe angle, could be explained in terms of a combination of two conflicting interactions between NH2 and μ-O(H) groups, that is, a steric repulsion and a hydrogen-bonding interactions. The LMCT bands of μ-O to iron(III) may be affected by hydrogen-bonding interactions between NH and μ-O(H) groups, which are discussed in connection with the formation processes of compound Q and compound X in sMMO and RNR-R2, respectively.

  三种以FeIII2(μ-O)(μ-OH)为核心的新配合物，周围环绕着一个、两个和三个氨基，即(6-氨基-2-吡啶基甲基)双(吡啶基甲基)胺(MAPA)、双(合成了作为氢键位点的 6-氨基-2-吡啶基甲基）（吡啶基甲基）胺（BAPA）和三（6-氨基-2-吡啶基甲基）胺（TAPA），并通过电子吸收光谱和 X 射线表征射线衍射分析。它们的结构键参数，Fe-N(吡啶)、Fe-N(胺)和Fe-μ-O(H)键、Fe···Fe距离和Fe-O-Fe角，可以用以下术语解释： NH2 和 μ-O(H) 基团之间两种相互冲突的相互作用的组合，即空间排斥和氢键相互作用。 μ-O与铁(III)的LMCT谱带可能受到NH和μ-O(H)基团之间氢键相互作用的影响，结合sMMO和RNR中化合物Q和化合物X的形成过程对此进行了讨论分别为-R2。
• LZnX complexes of tripodal ligands with intramolecular RN–H hydrogen bonding groups: structural implications of a hydrogen bonding cavity, and of X/R in the hydrogen bonding geometry/strength
  作者：Juan C. Mareque Rivas、Ravi Prabaharan、Rafael Torres Martín de Rosales、Laurent Metteau、Simon Parsons

  DOI：10.1039/b407790c

  日期：——

  Tripodal ligands N(CH2Py)3−n(CH2Py-6-NHR)n (R = H, n = 1–3 L1–31–31–3, n = 0 tpa; R = CH2tBu, n = 1–3 L′1–3′1–3′1–3) are used to investigate the effect of different hydrogen bonding microenvironments on structural features of their LZnX complexes (X = Cl−, NO3−, OH−). The X-ray structures of [(L222)Zn(Cl)](BPh4) 2·0.5(H2O·CH3CN), [(L333)Zn(Cl)](BPh4) 3·CH3CN, [(L′111)Zn(Cl)](BPh4) 1′, [(L′222)Zn(Cl)](BPh4) 2′·CH3OH, and [(L′333)Zn(Cl)](BPh4) 3′ have been determined and exhibit trigonal bipyramidal geometries with intramolecular (internal) N–H⋯Cl–Zn hydrogen bonds. The structure of [(L′222)Zn(ONO2)]NO34′·H2O with two internal N–H⋯O–Zn hydrogen bonds has also been determined. The axial Zn–Cl distance lengthens from 2.275 Å in [(tpa)Zn(Cl)](BPh4) to 2.280–2.347 Å in 1–3, 1′–3′. Notably, the average Zn–Npy distance is also progressively lengthened from 2.069 Å in [(tpa)Zn(Cl)](BPh4) to 2.159 and 2.182 Å in the triply hydrogen bonding cavity of 3 and 3′, respectively. Lengthening of the Zn–Cl and Zn–Npy bonds is accompanied by a progressive shortening of the trans Zn–N bond from 2.271 Å in [(tpa)Zn(Cl)](BPh4) to 2.115 Å in 3 (2.113 Å in 3′). As a result of the triply hydrogen bonding microenvironment the Zn–Cl and Zn–Npy distances of 3 are at the upper end of the range observed for axial Zn–Cl bonds, whereas the axial Zn–N distance is one of shortest among N4 ligands that induce a trigonal bipyramidal geometry. Despite the rigidity of these tripodal ligands, the geometry of the intramolecular RN–H⋯X–Zn hydrogen bonds (X = Cl−, OH−, NO3−) is strongly dependent on the nature of X, however, on average, similar for R = H, CH2tBu.

  利用三足配体 N(CH2Py)3ân(CH2Py-6-NHR)n（R = H，n = 1â3 L1â31â31â3，n = 0 tpa；R = CH2tBu，n = 1â3 Lâ²1â3â²1â3â²1â3）研究了不同氢键微环境对其 LZnX 复合物（X = Clâ、NO3â、OHâ）结构特征的影响。(L222)Zn(Cl)](BPh4) 2Â-0.5(H2OÂ-CH3CN)、[(L333)Zn(Cl)](BPh4) 3Â-CH3CN、[(Lâ²111)Zn(Cl)](BPh4) 1â²、[(Lâ²222)Zn(Cl)](BPh4) 2â²Â-CH3OH、和[(Lâ²333)Zn(Cl)](BPh4) 3â²的结构已经确定，它们呈现出具有分子内（内部）NâHâ¯ClâZn氢键的三叉双锥体几何结构。此外，还确定了具有两个内部 NâHâ¯OâZn 氢键的 [(Lâ²222)Zn(ONO2)]NO34â²Â-H2O 结构。ZnâCl的轴向距离从[(tpa)Zn(Cl)](BPh4)中的2.275 Ã延长到1â3, 1â²â3â²中的2.280â2.347 Ã。值得注意的是，ZnâNpy的平均距离也从[(tpa)Zn(Cl)](BPh4)中的2.069 Ã逐渐延长到3和3â²的三氢键空腔中的2.159 Ã和2.182 Ã。随着 ZnâCl 和 ZnâNpy 键的延长，反式 ZnâN 键也逐渐缩短，从[(tpa)Zn(Cl)](BPh4) 中的 2.271 à 到 3 中的 2.115 Ã（3â² 中为 2.113 Ã）。由于存在三重氢键微环境，3 的 ZnâCl 和 ZnâNpy 间距处于轴向 ZnâCl 键所观察到的范围的上限，而轴向 ZnâN 间距则是诱导出三叉双锥几何结构的 N4 配体中最短的距离之一。尽管这些三足配体具有刚性，但分子内 RNâHâ¯XâZn 氢键（X = Clâ、OHâ、NO3â）的几何形状在很大程度上取决于 X 的性质，但平均而言，R = H、CH2tBu 时的几何形状相似。