4-amino-3,5-bis([(2-pyridylmethyl)amino]methyl)-4H-1,2,4-triazole | 849804-60-0

• 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: 4-amino-3,5-bis([(2-pyridylmethyl)amino]methyl)-4H-1,2,4-triazole
• 英文别名: 4-amino-3,5-bis{[(2-pyridylmethyl)amino]methyl}-4H-1,2,4-triazole；4-Amino-3,5-bis{[(2-pyridylmethyl)amino]methyl}-4h-1,2,4-triazole；3,5-bis[(pyridin-2-ylmethylamino)methyl]-1,2,4-triazol-4-amine
• CAS: 849804-60-0
• 化学式: C₁₆H₂₀N₈
• 分子量: 324.388
• InChiKey: MVYZCWTYUNWDNR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  107
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-amino-3,5-bis([(2-pyridylmethyl)amino]methyl)-4H-1,2,4-triazole 、 iron(II) chloride tetrahydrate 以 甲醇 为溶剂， 以30%的产率得到[Fe(II)2(4-amino-3,5-bis([(2-pyridylmethyl)amino]methyl)-4H-1,2,4-triazole)2]Cl4*4H2O
  参考文献：
  名称：

  Effect of Counteranion X on the Spin Crossover Properties of a Family of Diiron(II) Triazole Complexes [Fe^II₂(PMAT)₂](X)₄

  摘要：

  Seven diiron(II) complexes, [Fe-2(II)(PMAT)(2)](X)(4), varying only in the anion X, have been prepared, where PMAT is 4-amino-3,5-bis{[(2-pyridylmethyl)- amino]methyl}-4H-1,2,4-triazole and X = BF4-, (1), Cl- (2), PF6- (3), SbF6- (4), CF3SO3- (5), B(PhF)(4)(-) (6), and C16H33SO3- (7). Most were isolated as solvates, and the microcrystalline ([3], [4]center dot 2H(2)O, [5]center dot H2O, and [6]center dot 1/2MeCN) or powder ([2]center dot 4H(2)O, and [7]center dot 2H(2)O) samples obtained were studied by variable-temperature magnetic susceptibility and Mossbauer methods. A structure determination on a crystal of [2]center dot 2MeOH center dot H2O, revealed it to be a [LS-HS] mixed low spin (LS)-high spin (HS) state dinuclear complex at 90 K, but fully high spin, [HS-HS], at 293 K. In contrast, structures of both [5]center dot 3/4IPA center dot H2O and [7]center dot 1.6MeOH center dot 0.4H(2)O showed them to be [HS-HS] at 90 K, whereas magnetic and Mossbauer studies on [5]center dot H2O and [7]center dot 2H(2)O revealed a different spin state, [LS-HS], at 90 K, presumably because of the difference in solvation. None of these complexes undergo thermal spin crossover (SCO) to the fully LS form, [LS-LS]. The PF6- and SbF6- complexes, 3 and [4]center dot 2H(2)O, appear to be a mixture of [HS-LS] and [HS-HS] at low temperature, and undergo gradual SCO to [HS-HS] on warming. The CF3SO3- complex [5]center dot H2O undergoes gradual, partial SCO from [HS-LS] to a mixture of [HS-LS] and [HS-HS] at T-1/2 approximate to 180 K. The B(PhF)(4)(-) and C16H33SO3- complexes, [6]center dot 1/2MeCN and [7]center dot 2H(2)O, are approximately [LS-HS] at all temperatures, with an onset of gradual SCO with T-1/2>300 K.

  DOI：

  10.1021/ic200308k
• 作为产物：
  描述：

  2-氨甲基吡啶 在 sodium hydroxide 、 硫酸 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 34.0h， 生成 4-amino-3,5-bis([(2-pyridylmethyl)amino]methyl)-4H-1,2,4-triazole
  参考文献：
  名称：

  1,2,4-三唑基双（齿）配体TsPMAT和PMAT的合成和一些第一行过渡金属配合物。

  摘要：

  已经研究了采用基于亲核取代而不是席夫碱缩合的策略来制备1,2,4-三唑基配体，并导致了两种新配体的合成，即4-氨基-3， 5-双{[N-（2-吡啶基甲基）-N-（4-甲苯磺酰基）氨基]甲基} -4H-1,2,4-三唑（TsPMAT，14）和4-氨基-3,5-bis { [（2-吡啶基甲基）氨基]甲基} -4H-1,2,4-三唑（PMAT，15）。这些是掺入1,2,4-三唑单元的双（齿）配体的第一个实例。TsPMAT（14）与Co（BF4）2.6 H2O形成双核2：2络合物，即使当金属与配体的摩尔比为2：1时也是如此。同样，PMAT（15）与Mn（ClO4）2.6H2O或M（BF4）2.6 H2O（M = Fe，Co，Ni，Zn）配体与金属的摩尔比为1：1的反应提供了通式[M（II）（2）（PMAT）2] X4的一系列配合物。TsPMAT（14）和PMAT（15）的这些络合物中的金属中心被两个配体分子包裹，并被1

  DOI：

  10.1002/chem.200500387

文献信息

• The first X-ray crystal structure determination of a dinuclear complex trapped in the [low spin–high spin] state: [Fe^II₂(PMAT)₂](BF₄)₄·DMF
  作者：Marco H. Klingele、Boujemaa Moubaraki、John D. Cashion、Keith S. Murray、Sally Brooker

  DOI：10.1039/b415891a

  日期：——

  The two metal centres in the doubly 1,2,4-triazole-bridged spin crossover complex [FeII2(PMAT)2](BF4)4·DMF (1·DMF) are trapped in different spin states below ca. 200 K, with no evidence that this particular [LS–HS] species can be converted into the [LS–LS] form at ambient pressure.

  在双1,2,4-噁唑桥接的自旋交叉复合物[FeII2(PMAT)2](BF4)4·DMF (1·DMF)中，两个金属中心在大约200 K以下被锁定在不同的自旋态，且没有证据表明这种特定的[低自旋-高自旋]物质可以在常压下转变为[低自旋-低自旋]形式。
• Effect of Counteranion X on the Spin Crossover Properties of a Family of Diiron(II) Triazole Complexes [Fe^II₂(PMAT)₂](X)₄
  作者：Jonathan A. Kitchen、Nicholas G. White、Guy N. L. Jameson、Jeffery L. Tallon、Sally Brooker

  DOI：10.1021/ic200308k

  日期：2011.5.16

  Seven diiron(II) complexes, [Fe-2(II)(PMAT)(2)](X)(4), varying only in the anion X, have been prepared, where PMAT is 4-amino-3,5-bis[(2-pyridylmethyl)- amino]methyl}-4H-1,2,4-triazole and X = BF4-, (1), Cl- (2), PF6- (3), SbF6- (4), CF3SO3- (5), B(PhF)(4)(-) (6), and C16H33SO3- (7). Most were isolated as solvates, and the microcrystalline ([3], [4]center dot 2H(2)O, [5]center dot H2O, and [6]center dot 1/2MeCN) or powder ([2]center dot 4H(2)O, and [7]center dot 2H(2)O) samples obtained were studied by variable-temperature magnetic susceptibility and Mossbauer methods. A structure determination on a crystal of [2]center dot 2MeOH center dot H2O, revealed it to be a [LS-HS] mixed low spin (LS)-high spin (HS) state dinuclear complex at 90 K, but fully high spin, [HS-HS], at 293 K. In contrast, structures of both [5]center dot 3/4IPA center dot H2O and [7]center dot 1.6MeOH center dot 0.4H(2)O showed them to be [HS-HS] at 90 K, whereas magnetic and Mossbauer studies on [5]center dot H2O and [7]center dot 2H(2)O revealed a different spin state, [LS-HS], at 90 K, presumably because of the difference in solvation. None of these complexes undergo thermal spin crossover (SCO) to the fully LS form, [LS-LS]. The PF6- and SbF6- complexes, 3 and [4]center dot 2H(2)O, appear to be a mixture of [HS-LS] and [HS-HS] at low temperature, and undergo gradual SCO to [HS-HS] on warming. The CF3SO3- complex [5]center dot H2O undergoes gradual, partial SCO from [HS-LS] to a mixture of [HS-LS] and [HS-HS] at T-1/2 approximate to 180 K. The B(PhF)(4)(-) and C16H33SO3- complexes, [6]center dot 1/2MeCN and [7]center dot 2H(2)O, are approximately [LS-HS] at all temperatures, with an onset of gradual SCO with T-1/2>300 K.
• Synthesis and Some First-Row Transition-Metal Complexes of the 1,2,4-Triazole-Based Bis(terdentate) Ligands TsPMAT and PMAT
  作者：Marco H. Klingele、Boujemaa Moubaraki、Keith S. Murray、Sally Brooker

  DOI：10.1002/chem.200500387

  日期：2005.11.18

  octahedral, as evidenced by the X-ray crystal structure analyses of [Co(II) (2)(TsPMAT)(2)](BF(4))(4)6 MeCN (246 MeCN) and [Fe(II) 2(PMAT)2](BF4)4DMF (27DMF). Studies of the magnetic properties of [Co(II) 2(TsPMAT)2](BF4)4.4 H2O (244 H2O), [Mn(II) 2(PMAT)2](ClO4)4 (26), and [Co(II) 2(PMAT)2](BF4)4 (28) have revealed weak antiferromagnetic coupling (J=-3.3, -0.16, and -2.4 cm(-1), respectively) between the two

  已经研究了采用基于亲核取代而不是席夫碱缩合的策略来制备1,2,4-三唑基配体，并导致了两种新配体的合成，即4-氨基-3， 5-双[N-（2-吡啶基甲基）-N-（4-甲苯磺酰基）氨基]甲基} -4H-1,2,4-三唑（TsPMAT，14）和4-氨基-3,5-bis [（2-吡啶基甲基）氨基]甲基} -4H-1,2,4-三唑（PMAT，15）。这些是掺入1,2,4-三唑单元的双（齿）配体的第一个实例。TsPMAT（14）与Co（BF4）2.6 H2O形成双核2：2络合物，即使当金属与配体的摩尔比为2：1时也是如此。同样，PMAT（15）与Mn（ClO4）2.6H2O或M（BF4）2.6 H2O（M = Fe，Co，Ni，Zn）配体与金属的摩尔比为1：1的反应提供了通式[M（II）（2）（PMAT）2] X4的一系列配合物。TsPMAT（14）和PMAT（15）的这些络合物中的金属中心被两个配体分子包裹，并被1