[2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine | 495417-60-2

• 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: [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine
• 英文别名: 1-[6-[[bis(pyridin-2-ylmethyl)amino]methyl]pyridin-2-yl]-N,N-bis(pyridin-2-ylmethyl)methanamine
• CAS: 495417-60-2
• 化学式: C₃₁H₃₁N₇
• 分子量: 501.634
• InChiKey: HDRDWMXZQKLJGI-UHFFFAOYSA-N

物化性质

• 沸点：
  606.8±50.0 °C(Predicted)
• 密度：
  1.218±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  70.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  manganese(II) perchlorate hexahydrate 、 [2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine 在 LiClO₄ 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 以74%的产率得到[Mn(κ7-N,N,N'N'-tetrakis(2-pyridylmethyl)-2,6-bis(aminomethyl)pyridine)](ClO4)2
  参考文献：
  名称：

  Fluxionality in a Paramagnetic Seven-Coordinate Iron(II) Complex: A Variable-Temperature, Two-Dimensional NMR and DFT Study

  摘要：

  The preparation and detailed characterizations of the high-spin seven-coordinate complexes [M(kappa N-7-L)](ClO4)(2) (M = Mn (II), Fe(II); L = N,N,N',N'-tetrakis(2-pyridylmethyl)-2,6-bis(aminomethyl)pyridine) are described. The X-ray crystal structures reveal seven-coordinate metal complex ions. Consideration of continuous shape measures reveals that the coordination environments about the metal ions are better described as having (C-s) face-capped trigonal prismatic symmetry than (C-2) pentagonal bipyramidal symmetry. The (S=5/2) Mn(II) species shows complicated X-band electron paramagnetic resonance (EPR) spectra and broad unrevealing H-1 NMR spectra. In contrast, the (S=2) Fe(II) complex is EPR-silent and shows completely interpretable H-1 NMR spectra containing the requisite number of paramagnetically shifted peaks in the range delta +150 to -60. The C-13 NMR spectra are likewise informative. Variable-temperature H-1 NMR spectra show coalescences and decoalescences indicative of an intramolecular process that pairwise-exchanges the nonequivalent pyridylmethyl "arms" of the two bis(pyridylmethyl)amine (bpa) domains. A suite of NMR techniques, including T-1 relaxation measurements and variable-temperature H-1-H-1 correlation spectroscopy, H-1-H-1 total correlation spectroscopy, H-1-H-1 nuclear Overhauser effect spectroscopy/exchange spectroscopy, and H-1 - C-13 heteronuclear multiple-quantum coherence experiments, has been used to assign the NMR spectra and characterize the exchange process. Analysis of the data from these experiments yields the following thermodynamic parameters for the exchange: Delta H-double dagger = 53.6 +/- 2.8 kJ mol(-1), Delta S-double dagger = -10.0 +/- 9.8 J K-1 mol(-1), and AGE (298 K) = 50.6 kJ mol(-1). Density functional theory (B3LYP) calculations have been used to explore the energetics of possible mechanistic pathways for the underlying fluxional process. The most plausible mechanism found involves dissociation of a pyridylmethyl arm to afford a strained six-coordinate species followed by rebinding of the arm in a different position to afford a new seven-coordinate transition state in which the pyridylmethyl arms within each bpa domain are essentially equivalent; the calculated energy barrier for this process is 53.5 kJ mol(-1), in good agreement with the observations.

  DOI：

  10.1021/ic900233d
• 作为产物：
  描述：

  2,6-bis[(tosyloxy)methyl]pyridine 、 二甲基吡啶胺 在 四乙基溴化铵 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到[2,6-bis[bis(2-pyridylmethyl)amino]methyl]-pyridine
  参考文献：
  名称：

  Strain-induced substitutional lability in a Ru(ii) complex of a hypodentate polypyridine ligand

  摘要：

  分离出了七价 N,N,N′,N′-四(2-吡啶基甲基)-2,6-双(氨基甲基)吡啶(tpap)的钌(II)络合物，即六氟磷酸盐络合物 Ru(tpap)(PF6)2。目前已经确定了 Ru(tpap)(CF3SO3)2-2H2O的晶体结构，它在单斜空间群 P21/n 中结晶。对 5894 个观察到的反射进行了结构细化，最终 R 值为 0.0549。七齿配体与六个硝基配位，即与两个叔硝基和四个吡啶硝基配位，其中一个吡啶未配位。由此产生的结构与八面体几何结构相比发生了明显的扭曲，Nsp3-Ru-Npyridine 的赤道夹角为 120°。上述立体应变的结果是系统的唇化，通过 1H NMR 观察到，在 d6 丙酮溶液中，Ru(tpap)(PF6)2 在赤道配位和非配位吡啶之间发生了交换。根据核磁共振实验确定了活化参数：ΔG≠298 = 53 kJ mol-1，ΔH≠ = 56 ± 1 kJ mol-1，ΔS≠ = -10 ± 3 J mol-1 K-1。此外，还运用密度泛函理论（DFT）进行了电子结构计算，以确定过渡态并估算活化势垒。在核磁共振和 DFT 结果的基础上，提出了涉及七配位中间体的等交换机制。

  DOI：

  10.1039/b316093a

文献信息

• Novel one-dimensional structures and solution behaviour of copper(ii) bromide and chloride complexes of a new pentapyridyldiamine ligandElectronic supplementary information (ESI) available: Table S1: Selected bands from FTIR spectra of solid-state species in KBr disks. Table S2: UV-Vis-NIR spectroscopic data. Fig. S1: Views of the crystal structure of [Cu2(L)Br3]2[Cu2Br4], illustrating: (a) the chains of bromide-bridged [Cu2(L)Br2]2+ tectons and interspersed [Cu2Br4]2? counter ions; (b) the packing of the chains and [Cu2Br4]2? counter ions. See http://www.rsc.org/suppdata/dt/b3/b315202b/
  作者：David G. Lonnon、Donald C. Craig、Stephen B. Colbran、Paul V. Bernhardt

  DOI：10.1039/b315202b

  日期：——

  Copper(II) bromide and chloride complexes of the new heptadentate ligand 2,6-bis(bis(2-pyridylmethyl)amino)methylpyridine (L) have been prepared. For the bromide complexes, chains of novel, approximately C2-symmetric, chiral [Cu2(L)Br2]2+ ‘wedge-shaped’ tectons are found. The links between the dicopper tectons and the overall chirality and packing of the chains are dictated by the bromide ion content

  溴化铜（II） 和新七齿的氯化物络合物 配体 2,6-双（双（2-吡啶基甲基）氨基）甲基吡啶（L）已经准备好了。对于溴化物络合物，发现了新型的，近似为C 2对称的，手性[Cu 2（L）Br 2 ] 2+ 楔形的构造链。双铜构成物与链的整体手性和堆积之间的联系由溴离子含量而不是抗衡阴离子决定。相比之下，氯化物络合物显示具有不同的N 3 CuCl 2和N 4 CuCl 2的连锁不对称[Cu 2（L）Cl 3 ] +构造。居中于固体。溴化双铜和氯化物单元的整体结构在溶液中保持不变，而与卤化物。还描述了各种物质的氧化还原化学。
• Copper(II)–azido complexes constructed from polypyridyl amine ligands
  作者：Franz A. Mautner、Masayuki Koikawa、Masahiro Mikuriya、Emily V. Harrelson、Salah S. Massoud

  DOI：10.1016/j.poly.2013.04.033

  日期：2013.8

  polymer Cu(II) complex bridged by perchlorate ions and azide ligand with the structural formula [Cu(DPA)(N3)(μO,O–ClO4)]n (1), [Cu(Ldpdmen)(μ1,3-N3)]ClO4}n (2), [Cu2(μ-Lpy)(μ-1,1,3-N3)(μ-1,3-N3)](ClO4)2}n (3) and [Cu2(LT)(μ2-1,3-N3)(N3)(H2O)](ClO4)2H2O}n (4) where DPA = di(2-pyridylmethyl)amine, Ldpdmen = N,N′-bis(2-pyridylmethyl)-N,N′-dimethylethylenediamine and Lpy = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]pyridine

  一种由高氯酸根离子和叠氮化物配体桥接的新型一维聚合物Cu（II）配合物，其结构式为[Cu（DPA）（N 3）（μO，O–ClO 4）] n（1），[Cu（L dpdmen）（μ1,3-N 3）] CLO 4 } ñ（2），[铜2（μ-L的py）（μ-1,1,3--N 3）（μ1,3-N 3）]（CLO 4）2 } ñ（3）和[铜2（L Ť）（μ 2 -1,3-N 3）（N 3）（H 2O）]（ClO 4）2 H 2 O} n（4）其中DPA =二（2-吡啶基甲基）胺，L dpdmen  =  N，N'-双（2-吡啶基甲基）-N，N'-二甲基乙二胺和L PY  = 2,6-双[双（2-吡啶基甲基）氨基甲基]吡啶和L Ť  = 3,5-双[双（2-吡啶基甲基）氨基甲基]甲苯合成。通过光谱技术（红外和可见光）和单晶X射线晶体学对复合物进行表征。磁特性进行了测定为1 - 3在可变温度下（4.5-300
• Structure, magnetic anisotropy and relaxation behavior of seven-coordinate Co(<scp>ii</scp>) single-ion magnets perturbed by counter-anions
  作者：Gangji Yi、Chunyang Zhang、Wen Zhao、Huihui Cui、Lei Chen、Zhenxing Wang、Xue-Tai Chen、Aihua Yuan、Yuan-Zhong Liu、Zhong-Wen Ouyang

  DOI：10.1039/d0dt01232g

  日期：——

  trigonal prism and a capped octahedron, which is perturbed by the variation of the counter anions. Easy-plane magnetic anisotropies for all complexes were revealed via the analyses of the direct-current magnetic data and high-field electron paramagnetic resonance (HFEPR) spectra. They show slow magnetic relaxation under applied direct current field, which is similar to the previously reported complex [CoII(BPA-TPA)](BF4)2

  一系列单核七配位Co（II）配合物[Co II（BPA-TPA）]（ClO 4）2 ·H 2 O（2-ClO 4），[Co II（BPA-TPA）]（PF 6）2（3-PF 6）和[Co II（BPA-TPA）]（BPh 4）2（4-BPh 4）是基于配体2,6-双（双（2-吡啶基甲基）氨基）甲基吡啶（BPA-TPA）合成的，其结构已通过单晶X射线衍射表征。所有这些络合物的特征是在加盖的三棱柱和加盖的八面体之间存在中间配位多面体，该配位体受反荷阴离子的变化干扰。通过分析直流磁数据和高场电子顺磁共振（HFEPR）光谱，揭示了所有配合物的易平面磁各向异性。它们在施加的直流电场下显示出缓慢的磁弛豫，类似于先前报道的复合物[Co II（BPA-TPA）]（BF 4）2（1-BF 4）的三角棱镜。这项工作提供了一个通过更改抗衡阴离子来调节单离子磁体（SIM）属性的新示例。
• A capped trigonal prismatic cobalt(<scp>ii</scp>) complex as a structural archetype for single-ion magnets
  作者：Gangji Yi、Huihui Cui、Chunyang Zhang、Wen Zhao、Lei Chen、Yi-Quan Zhang、Xue-Tai Chen、You Song、Aihua Yuan

  DOI：10.1039/c9dt04881b

  日期：——

  Two mononuclear, seven-coordinate Co(ii) and Fe(ii) complexes [CoII(BPA-TPA)](BF4)2 (1-Co) and [FeII(BPA-TPA)](ClO4)2 (2-Fe) with a capped trigonal prismatic coordination geometry have been synthesized from the pentapyridyldiamine (BPA-TPA) ligand. 1-Co exhibits easy plane anisotropy in which slow magnetic relaxation is observed under a 1.0 kOe dc field. It is the first example of a single-ion magnet

  两种单核，七配位的Co（ii）和Fe（ii）配合物[CoII（BPA-TPA）]（BF4）2（1-Co）和[FeII（BPA-TPA）]（ClO4）2（2-Fe ）由五吡啶基二胺（BPA-TPA）配体合成了具有封端的三角棱柱配位几何结构。1-Co表现出容易的平面各向异性，其中在1.0 kOe dc磁场下观察到缓慢的磁弛豫。这是3d过渡金属离子的单离子磁体（SIM）的第一个示例，该离子具有封闭的三角棱柱形配置。2-Fe不是1.8 K的SIM卡。
• Pseudo-mono-axial ligand fields that support high energy barriers in triangular dodecahedral Dy(<scp>iii</scp>) single-ion magnets
  作者：Ben Zhang、Zhijie Cheng、Yingying Wu、Lei Chen、Rong Jing、Xingwei Cai、Chunhui Jiang、Yi-Quan Zhang、Aihua Yuan、Hui-Hui Cui、Zhao-Yang Li

  DOI：10.1039/d2sc03182e

  日期：——

  great significance for their practical applications. Indeed, Ln complexes with high coordination numbers are satisfactorily air stable. However, such geometries easily produce spherical ligand fields that minimize magnetic anisotropy. Herein, we report the preparation of three air-stable eight-coordinate mononuclear Dy(III) complexes with triangular dodecahedral geometries, namely, [Dy(BPA-TPA)Cl](BPh4)2

  空气稳定的高性能单分子磁体（SMM）的合成对其实际应用具有重要意义。事实上，具有高配位数的 Ln 配合物具有令人满意的空气稳定性。然而，这种几何结构很容易产生球形配体场，从而最大限度地减少磁各向异性。在此，我们报道了三种具有三角形十二面体几何形状的空气稳定八坐标单核 Dy( III ) 配合物的制备，即 [Dy(BPA-TPA)Cl](BPh 4 ) 2 ( 1 ) 和 [Dy(BPA- TPA)(X)](BPh 4 ) 2 · n CH 2 Cl 2 (X = CH 3 O −和n= 1 代表2 ; L = PhO −和n = 2 for 3 )，使用一个新的设计概念，其中庞大的七齿[2,6-双[双(2-吡啶基甲基)氨基]甲基]-吡啶 (BPA-TPA) 配体包裹 Dy ( III ) 离子通过弱配位键，仅留下一个小空位供带负电荷的 (Cl - )、甲氧基 (CH 3 O - ) 或苯氧基