3,5-bispyrazole | 172044-03-0

• 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: 3,5-bispyrazole
• 英文别名: 3,5-bis[N,N-bis(2-pyridylmethyl)aminomethyl]-1H-pyrazole；3,5-bis[N,N-di(2-pyridylmethyl)aminomethyl]pyrazole；N-[[3-[[bis(pyridin-2-ylmethyl)amino]methyl]-1H-pyrazol-5-yl]methyl]-1-pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine
• CAS: 172044-03-0
• 化学式: C₂₉H₃₀N₈
• 分子量: 490.611
• InChiKey: IUBPUVWBQCCKRG-UHFFFAOYSA-N

物化性质

• 沸点：
  642.9±50.0 °C(Predicted)
• 密度：
  1.258±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  86.7
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  甲醇 、 copper(II) tetrafluroborate hexahydrate 、 3,5-bispyrazole 在 KO(t)Bu 作用下， 以 甲醇 为溶剂， 以21%的产率得到
  参考文献：
  名称：

  Compartmental pyrazolate ligands providing two adjacent tris(pyridylalkyl)amine-type binding pockets and their dicopper(II) fluoride complexes featuring extremely short intramolecular O–H⋯F bridges

  摘要：

  A set of pyrazolate-based compartmental ligands HL2-HL5 with pendent (pyridylalkyl)amine side arms in the 3- and 5-positions of the pyrazole has been prepared. The ligands differ by the number and lengths of the pyridylalkyl arms, and they can be described as dinucleating versions of well-known ligands such as tris(pyridylmethyl)amine (tpma) or tris(pyridylethyl)amine (tpea). Reaction of HL2, HL3 or HL5 with Cu(BF4)(2).6H(2)O in the presence of base causes fluoride abstraction from the tetrafluoroborate and gives dicopper(II) complexes 1, 2, and 3a and b, respectively, which feature extremely short intramolecular F...HOMe or F...HOH bridges (d(F...O) = 2.384(6)-2.507(3)). Molecular structures of all four complexes have been elucidated by X-ray crystallography and are compared to their mononuclear analogues. The influence of the intramolecular F...HO bridge on Cu F and Cu-O bond lengths as well as on other structural characteristics is discussed. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2004.04.023
• 作为产物：
  描述：

  二甲基吡啶胺 、 3,5-bis(chloromethyl)pyrazolium chloride 反应 2.0h， 生成 3,5-bispyrazole
  参考文献：
  名称：

  μ-吡唑并合-羧基和二（吡唑并合）二锰（II）配合物：合成，表征和过氧化氢酶样功能

  摘要：

  3,5-双[ N，N-二（2-吡啶基甲基）氨基甲基]吡唑（HL 1）和3,5-双[ N，N-双（2-二乙基氨基乙基）氨基甲基]吡唑（HL 2）形成µ-吡唑并-羧甲基二锰（II）配合物[Mn 2 L（O 2 CR）] [BPh 4 ] 2（L = L 1，R = Ph; 1 ; L = L 2，R = Me 2）和3 ，5-双[ N-（2-吡啶基甲基）氨基甲基]吡唑（HL 3）得到二（µ-吡唑并合）-二锰（II）配合物[Mn 2 L3 2 ] [BPh 4 ] 2 3。3的二甲苯加合物在三斜空间群P中结晶， a = 14.452（3）， b = 15.573（5）， c = 10.988（4）Å，α= 108.78（3），β= 93.31（2）和γ = 115.10（2）°。X射线衍射分析显示二（µ-吡唑并合）-二锰（ II）核，Mn Mn分离度为4.181（2）Å。所有的配合物在0℃下均表现出对H

  DOI：

  10.1039/dt9950003635

文献信息

• Structural Flexibility of Carboxylate Bridging Exemplified by a Series of μ-Acetato Dizinc Complexes
  作者：Miguel Alvariño Gil、Walter Maringgele、Sebastian Dechert、Franc Meyer

  DOI：10.1002/zaac.200700200

  日期：2007.10

  A series of closely related dizinc acetato complexes [LZn2(OAc)](ClO4)2 has been prepared from an assortment of known (HL1 – HL3) and new (HL4 – HL6) binucleating compartmental pyrazolate-based ligands that provide two tripodal tetradentate N4}-type binding pockets but differ by the type of N-donor within the chelate side arms. Six complexes 1a, 1b, 2 – 5 have been characterized by X-ray crystallography

  一系列密切相关的乙酰二锌配合物 [LZn2 (OAc)] (ClO4) 2 已从各种已知的 (HL1 - HL3) 和新的 (HL4 - HL6) 双核区室吡唑酸盐基配体制备，提供两个三足四齿 N4} 型结合口袋，但因螯合侧臂内 N 供体的类型而异。六个配合物 1a、1b、2-5 已通过 X 射线晶体学表征。在所有情况下，两个锌离子都是五配位的，如预期的那样嵌套在相邻的配体隔室中，并由位于双金属口袋内的 μ1,3-桥接醋酸盐跨越。从结构数据推断 μ1,3-乙酰基配体具有显着的灵活性，导致金属离子错位出吡唑酸盐平面以及乙酸桥相对于双金属支架的严重扭曲和倾斜。与从称为“羧酸盐位移”的动态行为已知的不同乙酸盐结合模式相比，这些不同方向的桥接乙酸盐不能通过它们的红外光谱来区分。然而，μ1,3-乙酸盐的高度灵活性即使其配位模式没有改变也很可能是乙酸盐桥联双金属排列反应模式的先决条件。
• Intra‐ and Intermolecular H···Cl–Ni Bonding Patterns in a Series of Highly Preorganized Dinuclear Nickel(II) Complexes
  作者：Feng‐Mei Nie、Guido Leibeling、Serhiy Demeshko、Sebastian Dechert、Franc Meyer

  DOI：10.1002/ejic.200600889

  日期：2007.3

  Four dinickel complexes [L1Ni2(μ-Cl)(Cl)2]·2CH3OH (1a), [L1Ni2(μ-Cl)(CH3OH)](ClO4)2 (1b), [L2Ni2(μ-Cl)Cl2(H2O)2]·H2O (2) and [L3Ni2Cl2(CH3OH)2]Cl·2CH3OH (3) were synthesized and structurally characterized. The ligand scaffolds have a central pyrazolato bridge and N-donor chelate arms that provide two proximate binding pockets for the nickel ions. While the longer ligand side arms in 1a, 1b and 2 induce

  四种二镍配合物 [L1Ni2(μ-Cl)(Cl)2]·2CH3OH (1a), [L1Ni2(μ-Cl)(CH3OH)](ClO4)2 (1b), [L2Ni2(μ-Cl)Cl2(H2O) )2]·H2O (2) 和 [L3Ni2Cl2(CH3OH)2]Cl·2CH3OH (3) 被合成和结构表征。配体支架具有中央吡唑啉桥和 N 供体螯合臂，为镍离子提供两个邻近的结合袋。虽然 1a、1b 和 2 中较长的配体侧臂诱导 Ni…Ni 距离约为 4.0 A 并有利于在双金属口袋内结合氯桥，但拉伸的 Ni…Ni 分离为 4.6 A，具有不寻常的分子内在 3 中观察到 Cl···H-O 键。在 1-3 的固态结构中发现了各种 Cl···H-O 氢键基序，其中 H 供体（MeOH 或 H2O）或H-受体（氯）或两者都与镍离子结合，并讨论了它们的相对供体-受体距离。通过吡唑和氯桥介导的磁耦合相当弱和反铁磁性，但对于
• Bridging β‐Lactam Coordination at Dinuclear Zinc Sites
  作者：Franc Meyer、Hans Pritzkow

  DOI：10.1002/ejic.200401032

  日期：2005.6

  weakening of the C=O bond relative to free 2-azetidinone. These findings contrast the reverse geometrical changes observed recently by Brombacher and Vahrenkamp for β-lactamide N-bound to only a single zinc ion, thus underlining the particular dimetallic effect that is achieved by the cooperativity of two adjacent metal ions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  发现两个基于隔室吡唑酸盐配体的高度预组织的二锌支架在其去质子化的 β-内酰胺形式中结合了 2-氮杂环丁酮作为双金属口袋内的 N,O-桥连配体。二锌 β-内酰胺配合物 3·(ClO4)2 和 4·(ClO4)2 已在结构和光谱上进行了表征，揭示了 β-内酰胺 C-N 键的增强和 C=O 键相对于游离键的减弱。 2-氮杂环丁酮。这些发现与 Brombacher 和 Vahrenkamp 最近观察到的 β-内酰胺 N 仅与单个锌离子结合的反向几何变化形成对比，从而强调了通过两个相邻金属离子的协同作用实现的特殊双金属效应。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Two dinuclear iron(ii) complexes K[Fe2(L1)(SCN)4]·2(C3H8O) and [Fe2(L1)(SeCN)3(C5H5N)]·H2O are stabilised in the ‘[HS–LS]’ state by a bis-tetradentate pyrazolate-based ligand
  作者：Juan Olguín、Guy N. L. Jameson、Sally Brooker

  DOI：10.1039/c0dt01391a

  日期：——

  Two air-sensitive dinuclear iron(II) complexes, K[FeII2(L1)(SCN)4]·2(C3H8O) (1) and [FeII2(L1)(SeCN)3(C5H5N)]·H2O (2), of 3,5-bis[N,N-bis(2-pyridylmethyl)aminomethyl]-1H-pyrazolate [(L1)−] have been prepared. Interestingly, complex 1 is anionic, featuring four coordinated SCN− anions and a potassium counterion whereas complex 2 is neutral, containing a coordinated pyridine molecule and only three coordinated SeCN− anions. These are the first iron complexes reported for this type of ligand. Magnetic measurements and Mössbauer spectra show that both 1 and 2 are in a ‘[HS–LS]’ mixed spin state between 300 and 2 K.

  两种空气敏感双核铁(II)配合物，K[FeII2(L1)(SCN)4]·2(C3H8O) (1) 和 [FeII2(L1)(SeCN)3(C5H5N)]·H2O (2 ），3,5-双[N,N-双（2-吡啶甲基）氨基甲基]-1H-吡唑酯[(L1)-]已制备。有趣的是，配合物 1 是阴离子的，具有四个配位的 SCN- 阴离子和一个钾抗衡离子，而配合物 2 是中性的，包含一个配位的吡啶分子和仅三个配位的 SeCN- 阴离子。这是首次报道此类配体的铁配合物。磁测量和穆斯堡尔谱表明，1 和 2 在 300 到 2 K 之间均处于 α[HSβLS]α 混合自旋态。
• Magnetostructural correlations in μ-pyrazolato-μ-acetato dinickel(II) complexes: Subtle effects of acetate tilting
  作者：Feng-Mei Nie、Guido Leibeling、Serhiy Demeshko、Sebastian Dechert、Franc Meyer

  DOI：10.1016/j.ica.2008.03.101

  日期：2009.2

  A series of dinickel acetato complexes [LNi2(OAc)(solvent)(x)](ClO4)(2) (1-3, 5) as well as related complexes [LNi2(OAc)(2)](OAc) (4) and [LNi2(OAc)( NO3)(2)] (6), all derived from three pyrazolate-based binucleating ligands, have been prepared and characterized by X-ray crystallography. The solid state structures reveal different acetate binding modes (mu(1,3)-bridging and bidentate chelating) plus severe twisting and tilting of the mu(1,3)-acetate bridges with respect to their bimetallic scaffolds, reflecting the great flexibility of carboxylate coordination. Magnetic properties of all six complexes have been investigated, and the strength of antiferromagnetic coupling is discussed in the light of the structural differences, suggesting a magneto-structural correlation for acetato-bridged complexes. (C) 2008 Elsevier B. V. All rights reserved.