3,5-bispyrazole | 172044-04-1

• 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: 3,5-bispyrazole
• 英文别名: 3,5-bis([N-(2-pyridylmethyl)amino]methyl)-1H-pyrazole；3,5-bis{[N-(2-pyridylmethyl)amino]methyl}-1H-pyrazole；3,5-bis[N-(2-pyridylmethyl)aminomethyl]pyrazole；PMAPH；1-pyridin-2-yl-N-[[3-[(pyridin-2-ylmethylamino)methyl]-1H-pyrazol-5-yl]methyl]methanamine
• CAS: 172044-04-1
• 化学式: C₁₇H₂₀N₆
• 分子量: 308.386
• InChiKey: BUXVNOCJSGPZNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  78.5
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  copper(II) tetrafluroborate hexahydrate 、 3,5-bispyrazole 在 Et₃N 作用下， 以 乙腈 为溶剂， 以63%的产率得到[Cu2(3,5-bis([N-(2-pyridylmethyl)amino]methyl)-1H-pyrazolate)2](BF4)2*H2O
  参考文献：
  名称：

  Doubly Pyrazolate-Bridged Dinuclear Complexes of a Highly Constrained Bis-terdentate Ligand: Observation of a [High Spin-Low Spin] State for [Fe^II₂(PMAP)₂][SbF₆]₂·2.25(C₃H₈O) (PMAP = 3,5-bis{[N-(2-pyridylmethyl)amino]-methyl}-1H-pyrazolate)

  摘要：

  The bis-terdentate pyrazole-based ligand 3,5-bis{[N-(2-pyridylmethyl)amino]methyl}-1H-pyrazole (PMAPH) was synthesized from 3,5-(1H)-pyrazoledicarbaldehyde and 2 equiv of 2-(aminomethyl)pyridine, using sodium borohydride to reduce the imine intermediate. A family of dinuclear complexes [M-2(II/III)(PMAP)(2)](X)(2/4) was prepared by 2:2:2 reactions of MX2/PMAPH/base, where M = Zn-II and X = BF4-; M = Cu-II and X = ClO4-, BF4-, OAc-, NO3-; M = Ni-II, Fe-III and X = ClO4-, BF4-; M = Fe-II and X = SbF6-. Single crystal X-ray structure determinations on four complexes: [Fe-2(III)(PMAP)(2)](BF4)(2)center dot 2MeCN, [Ni-2(II)(PMAP)(2)](ClO4)(2)center dot 2MeCN, [Cu-2(II)(PMAP)(2)](BF4)(2)center dot 2MeCN, and [Zn-2(II)(PMAP)(2)](BF4)(2)center dot 2MeCN confirmed a dinuclear doubly pyrazolate-bridged structure for each. The two metal centers in these complexes have similar N-6 distorted octahedral coordination spheres, with all donors provided by the two deprotonated PMAP(-) ligands. Magnetic measurements reveal intra-dinuclear antiferromagnetic interactions for both the M = Cu-II and Ni-II [M-2(PMAP)(2)](BF4)(4) complexes, with J/k(B) = 252(2) K and J/k(B) = -24.7(2) K (H = -2JS(M)S(M)), respectively. Interestingly magnetic measurements show that the complex [Fe-2(II)(PMAP)(2)](SbF6)(2)center dot 2.25(C3H8O) is in a mixed high spin (HS)-low spin (LS) spin state, [HS-LS], from 300 to 1.8K, with no sign of spin crossover to a fully low spin form [LS-LS] even at 1.8 K.

  DOI：

  10.1021/ic1001013
• 作为产物：
  描述：

  在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 1.25h， 生成 3,5-bispyrazole
  参考文献：
  名称：

  Doubly Pyrazolate-Bridged Dinuclear Complexes of a Highly Constrained Bis-terdentate Ligand: Observation of a [High Spin-Low Spin] State for [Fe^II₂(PMAP)₂][SbF₆]₂·2.25(C₃H₈O) (PMAP = 3,5-bis{[N-(2-pyridylmethyl)amino]-methyl}-1H-pyrazolate)

  摘要：

  The bis-terdentate pyrazole-based ligand 3,5-bis{[N-(2-pyridylmethyl)amino]methyl}-1H-pyrazole (PMAPH) was synthesized from 3,5-(1H)-pyrazoledicarbaldehyde and 2 equiv of 2-(aminomethyl)pyridine, using sodium borohydride to reduce the imine intermediate. A family of dinuclear complexes [M-2(II/III)(PMAP)(2)](X)(2/4) was prepared by 2:2:2 reactions of MX2/PMAPH/base, where M = Zn-II and X = BF4-; M = Cu-II and X = ClO4-, BF4-, OAc-, NO3-; M = Ni-II, Fe-III and X = ClO4-, BF4-; M = Fe-II and X = SbF6-. Single crystal X-ray structure determinations on four complexes: [Fe-2(III)(PMAP)(2)](BF4)(2)center dot 2MeCN, [Ni-2(II)(PMAP)(2)](ClO4)(2)center dot 2MeCN, [Cu-2(II)(PMAP)(2)](BF4)(2)center dot 2MeCN, and [Zn-2(II)(PMAP)(2)](BF4)(2)center dot 2MeCN confirmed a dinuclear doubly pyrazolate-bridged structure for each. The two metal centers in these complexes have similar N-6 distorted octahedral coordination spheres, with all donors provided by the two deprotonated PMAP(-) ligands. Magnetic measurements reveal intra-dinuclear antiferromagnetic interactions for both the M = Cu-II and Ni-II [M-2(PMAP)(2)](BF4)(4) complexes, with J/k(B) = 252(2) K and J/k(B) = -24.7(2) K (H = -2JS(M)S(M)), respectively. Interestingly magnetic measurements show that the complex [Fe-2(II)(PMAP)(2)](SbF6)(2)center dot 2.25(C3H8O) is in a mixed high spin (HS)-low spin (LS) spin state, [HS-LS], from 300 to 1.8K, with no sign of spin crossover to a fully low spin form [LS-LS] even at 1.8 K.

  DOI：

  10.1021/ic1001013

文献信息

• µ-Pyrazolato-µ-carboxylato- and di(µ-pyrazolato)dimanganese(<scp>II</scp>) complexes: synthesis, characterization and catalase-like function
  作者：Makoto Itoh、Ken-ichiro Motoda、Kenji Shindo、Toshiro Kamiusuki、Hiroshi Sakiyama、Naohide Matsumoto、Hisashi Ōkawa

  DOI：10.1039/dt9950003635

  日期：——

  N-di(2-pyridylmethyl)aminomethyl]pyrazole (HL1) and 3,5-bis[N,N-bis(2-diethylaminoethyl)aminomethyl]pyrazole (HL2) formed µ-pyrazolato-µ-carboxylato-dimanganese(II) complexes [Mn2L(O2CR)][BPh4]2(L = L1, R = Ph; 1; L = L2, R = Me 2) and 3,5-bis[N-(2-pyridylmethyl)aminomethyl]pyrazole (HL3) gave a di(µ-pyrazolato)-dimanganese(II) complex [Mn2L32][BPh4]23. The ditoluene adduct of 3 crystallizes in the triclinic

  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
• Doubly Pyrazolate-Bridged Dinuclear Complexes of a Highly Constrained Bis-terdentate Ligand: Observation of a [High Spin-Low Spin] State for [Fe^II₂(PMAP)₂][SbF₆]₂·2.25(C₃H₈O) (PMAP = 3,5-bis{[<i>N</i>-(2-pyridylmethyl)amino]-methyl}-1<i>H</i>-pyrazolate)
  作者：Andy Noble、Juan Olguín、Rodolphe Clérac、Sally Brooker

  DOI：10.1021/ic1001013

  日期：2010.5.17

  The bis-terdentate pyrazole-based ligand 3,5-bis[N-(2-pyridylmethyl)amino]methyl}-1H-pyrazole (PMAPH) was synthesized from 3,5-(1H)-pyrazoledicarbaldehyde and 2 equiv of 2-(aminomethyl)pyridine, using sodium borohydride to reduce the imine intermediate. A family of dinuclear complexes [M-2(II/III)(PMAP)(2)](X)(2/4) was prepared by 2:2:2 reactions of MX2/PMAPH/base, where M = Zn-II and X = BF4-; M = Cu-II and X = ClO4-, BF4-, OAc-, NO3-; M = Ni-II, Fe-III and X = ClO4-, BF4-; M = Fe-II and X = SbF6-. Single crystal X-ray structure determinations on four complexes: [Fe-2(III)(PMAP)(2)](BF4)(2)center dot 2MeCN, [Ni-2(II)(PMAP)(2)](ClO4)(2)center dot 2MeCN, [Cu-2(II)(PMAP)(2)](BF4)(2)center dot 2MeCN, and [Zn-2(II)(PMAP)(2)](BF4)(2)center dot 2MeCN confirmed a dinuclear doubly pyrazolate-bridged structure for each. The two metal centers in these complexes have similar N-6 distorted octahedral coordination spheres, with all donors provided by the two deprotonated PMAP(-) ligands. Magnetic measurements reveal intra-dinuclear antiferromagnetic interactions for both the M = Cu-II and Ni-II [M-2(PMAP)(2)](BF4)(4) complexes, with J/k(B) = 252(2) K and J/k(B) = -24.7(2) K (H = -2JS(M)S(M)), respectively. Interestingly magnetic measurements show that the complex [Fe-2(II)(PMAP)(2)](SbF6)(2)center dot 2.25(C3H8O) is in a mixed high spin (HS)-low spin (LS) spin state, [HS-LS], from 300 to 1.8K, with no sign of spin crossover to a fully low spin form [LS-LS] even at 1.8 K.