4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1Himidazole-1-oxyl | 1259289-16-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1Himidazole-1-oxyl
• 英文别名: 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazol-1-oxyl
• CAS: 1259289-16-1
• 化学式: C₁₁H₁₇N₄O
• 分子量: 221.282
• InChiKey: GLYRZTLWCSKDKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  34.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1Himidazole-1-oxyl 、 copper(II) hexafluoroacetylacetonate 以 正己烷 、 二氯甲烷 为溶剂， 反应 168.0h， 以40%的产率得到[4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1Himidazole-1-oxyl-N]bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-O,O)copper(II)
  参考文献：
  名称：

  Crystals of the CuII complex with nitronyl nitroxide and imino nitroxide exhibiting mechanical activity

  摘要：

  作为能够表现出化学机械活性的多自旋化合物持续研究的一部分，一系列组成为 [Cu(hfac)2L x L'2−x ]、[Cu(hfac)2L']、[Cu2(Piv) 的异质自旋固体4L'2]·0.5C6H14 和 [Cu2(hfac)2(Piv)2L'2]，其中 hfac 是六氟乙酰丙酮阴离子，L 是 4,4,5,5-四甲基-2-(1-甲基-1H) -咪唑-5-基)-4,5-二氢-1H-咪唑-3-氧化物-1-氧基，L'是L的亚氨基硝基氧类似物，即4,4,5,5-四甲基-2合成并表征了-(1-甲基-1H-咪唑-5-基)-4,5-二氢-1H-咪唑-1-氧基，Piv是2,2-二甲基丙酸根阴离子。固溶体 [Cu(hfac)2L x L'2-x ] 的合成晶体的堆积（其中 L 占主导地位）与 [Cu(hfac)2L2] 的堆积类似，并且这些晶体能够进行化学机械运动。相反，[Cu(hfac)2L x L'2−x ]晶体（其中L'占主导地位）具有与[Cu(hfac)2L'2]相似的结构参数，并且不表现出热激活或光激活化学机械活动。

  DOI：

  10.1007/s11172-013-0260-5
• 作为产物：
  描述：

  2-(1-methylimidazol-5-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide-1-oxyl 在 硫脲 作用下， 以 甲醇 为溶剂， 生成 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1Himidazole-1-oxyl
  参考文献：
  名称：

  Electrochemistry of nitronyl and imino nitroxides

  摘要：

  Redox potentials of a wide group of azolyl-substituted nitronyl and imino nitroxides were determined by classic cyclic voltammetry (CV). Conclusions have been made for this group of compounds, and their peculiarities were emphasized in comparison with methyl-, phenyl-, iodo-, and cyano-substituted nitroxides.

  DOI：

  10.1134/s0036024409110284

文献信息

• Heterospin complexes of polynuclear NiII compounds containing hexafluoroacetylacetonate and pivalate ligands with nitroxides
  作者：E. Yu. Fursova、O. V. Kuznetsova、G. V. Romanenko、A. S. Bogomyakov、V. I. Ovcharenko

  DOI：10.1007/s11172-010-0084-5

  日期：2010.2

  The heterospin mixed-ligand complex [Ni6(OH)4Piv4(hfac)4(NIT-Ph)2] (1) (NIT-Ph is 4,4,5,5-tetramethyl-2-phenyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide, hfac is hexafluoroacetylacetonate, and Piv is pivalate) was synthesized. The method for the synthesis of complex 1 is based on the replacement of acetone molecules in the hexanuclear complex containing the hexafluoroacetylacetonate and pivalate ligands [Ni6(OH)4Piv4(hfac)4(Me2CO)4] by NIT-Ph molecules. Two monodentate NIT-Ph molecules replace four acetone molecules, because the coordination of the O atom of the nitroxide group results in the blocking of one of the positions in the coordination environment of NiII the access to which is hindered by the phenyl ring of NIT-Ph. As a result, these ions are in a square-pyramidal environment unusual of NiII. In the low-temperature range, the dependence of the magnetization of 1 on the magnetic field is described by the Brillouin function. The reaction of [Ni6Piv4(hfac)4(OH)4(Me2CO)4] with the nitronyl nitroxide radicals 4,4,5,5-tetramethyl-2-(4-pyridyl)-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide (NIT-p-Py) or 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide (NIT-Iz) containing the pyridine or 1-methylimidazol-5-yl substituent, respectively, in the side chain is accompanied by the decomposition of the polynuclear fragment and affords the mononuclear complexes Ni(hfac)2(NIT-p-Py)2 and Ni(hfac)2(NIT-Iz)2, respectively. The reaction of 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihyd-ro-1H-imidazol-1-oxyl (Im-Iz), which is the imine analog of NIT-Iz, with [Ni6Piv4(hfac)4(OH)4(Me2CO)4] afforded the decanuclear complex [Ni10(OH)8Piv4(hfac)8(Im-Iz)2(H2O)6]. The molecular and crystal structures of all heterospin compounds were determined, and the magnetic properties of all compounds were investigated in the 2–300 K temperature range.

  合成了杂质混合配体[Ni6(OH)4Piv4(hfac)4(NIT-Ph)2]（1）（NIT-Ph 是 4,4,5,5-四甲基-2-苯基-4,5-二氢-1H-咪唑-1-氧 3-氧化物，hfac 是六氟丙酮酸酯，Piv 是特戊酸酯）。复合物 1 的合成方法是用 NIT-Ph 分子取代含有六氟乙酰丙酮酸和特戊酸配体[Ni6(OH)4Piv4(hfac)4(Me2CO)4]的六核复合物中的丙酮分子。两个单齿 NIT-Ph 分子取代了四个丙酮分子，因为亚硝基的 O 原子配位导致 NiII 配位环境中的一个位置被阻断，NIT-Ph 的苯基环阻碍了该位置的进入。因此，这些离子处于与 NiII 不同的方阵环境中。在低温范围内，1 的磁化与磁场的关系用布里渊函数来描述。Ni6Piv4(hfac)4(OH)4(Me2CO)4] 与 4,4,5,5-四甲基-2-(4-吡啶基)-4,5-二氢-1H-咪唑-1-氧 3-氧化物（NIT-p-Py）或 4,4,5,5-四甲基-2-(1-甲基-1H-咪唑-5-基)-4、与侧链中分别含有吡啶或 1-甲基咪唑-5-基取代基的 4,4,5,5-四甲基-2-(1-甲基-1H-咪唑-5-基)-4,5-二氢-1H-咪唑-1-氧 3-氧化物 (NIT-Iz) 反应的同时，多核片段会发生分解，并分别生成单核络合物 Ni(hfac)2(NIT-p-Py)2 和 Ni(hfac)2(NIT-Iz)2。NIT-Iz的亚胺类似物4,4,5,5-四甲基-2-(1-甲基-1H-咪唑-5-基)-4,5-二氢-1H-咪唑-1-氧(Im-Iz)与[Ni6Piv4(hfac)4(OH)4(Me2CO)4]反应得到十核配合物[Ni10(OH)8Piv4(hfac)8(Im-Iz)2(H2O)6]。确定了所有异质旋化合物的分子和晶体结构，并研究了所有化合物在 2-300 K 温度范围内的磁性。
• Heterospin complexes based on cobalt semiquinolate with nitroxides
  作者：E. Yu. Fursova、O. V. Kuznetsova、E. V. Tretyakov、G. V. Romanenko、A. S. Bogomyakov、V. I. Ovcharenko、R. Z. Sagdeev、V. K. Cherkasov、M. P. Bubnov、G. A. Abakumov

  DOI：10.1007/s11172-011-0129-4

  日期：2011.5

  Heterospin complexes based on cobalt semiquinolate with stable nitroxides of composition [Co(SQ)2(NIT)2]·8CH2Cl2, [Co(SQ)2(NIT)2]·4MeCN, [Co(SQ)2(IN)2]·5Me2CO, [Co(SQ)2(IN)2]·4MeCN, and [Co(SQ)2(IN)2]·2CH2Cl2·C6H14, where SQ is 3,6-di-tert-butyl-o-benzosemiquinolate, NIT is 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, and IN is the imine analog of NIT, viz., 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-1-oxyl, were synthesized. The characteristic feature of these compounds is that they contain two different types of paramagnetic organic ligands. The X-ray diffraction study showed that the solid phases of the complexes have a molecular structure. According to the data from thermomagnetic analysis (2–350 K), all complexes exhibit effects of valence tautomerism at ∼20 °C. It was found that incorporated solvent molecules have an effect on the magnetic anomaly temperature.

  基于半喹啉酸钴与组成为[Co(SQ)2(NIT)2]-8CH2Cl2、[Co(SQ)2(NIT)2]-4MeCN、[Co(SQ)2(IN)2]-5Me2CO、[Co(SQ)2(IN)2]-4MeCN和[Co(SQ)2(IN)2]-2CH2Cl2-C6H14的稳定硝基的异质配合物、其中，SQ 是 3,6-二叔丁基-邻苯甲酰喹啉酸，NIT 是 4,4,5,5-四甲基-2-(1-甲基-1H-咪唑-5-基)-4,5-二氢-1H-咪唑-3-氧化物-1-氧乙基，IN 是 NIT 的亚胺类似物，即,合成了 4,4,5,5-四甲基-2-(1-甲基-1H-咪唑-5-基)-4,5-二氢-1H-咪唑-1-氧化物。这些化合物的特点是含有两种不同类型的顺磁性有机配体。X 射线衍射研究表明，这些复合物的固相具有分子结构。根据热磁性分析（2-350 K）的数据，所有配合物在 ∼20 °C 时都表现出价态同分异构的效应。研究发现，掺入的溶剂分子对磁异常温度有影响。
• “Jumping Crystals”: Oxygen-Evolving Metal-Nitroxide Complexes
  作者：Victor I. Ovcharenko、Sergei V. Fokin、Elena Yu. Fursova、Olga V. Kuznetsova、Eugene V. Tretyakov、Galina V. Romanenko、Artem S. Bogomyakov

  DOI：10.1021/ic1022483

  日期：2011.5.16

  The crystals of heterospin complexes [M(hfac)(2)L-2] (where M = Cu, Ni, Co, or Mn; hfac = hexafluoroacetylacetonate; and L = nitronyl nitroxide, 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl) were found to make unusual jumping motions. Under ambient conditions, the jumping and various displacements of crystals lasted for several weeks. The mechanical motion was accompanied by the cracking and disintegration of crystals, and a solid [M(hfac)(2)(L-f)(2)] complex with the corresponding imino nitroxide 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-l-oxyl (L-1) was detected. The jumping was accompanied by the spontaneous elimination of oxygen, the source of which was the nitronyl nitroxyl fragment of coordinated L. An X-ray study of [M(hfac)(2)L-2] (where M = Cu, Ni, Co, or Mn) showed that the molecular structure of all [M(hfac)(2)L-2] and their packing in the solid state were identical. The packing of [M(hfac)(2)L-2] was concluded to be critical to the mechanical effect. In complexes with different stoichiometries or different sets of diamagnetic ligands ([Cu(hfac)(2)L](2), [Cu(hfac)(acac)L] center dot EtOH, [CuPiv(2)L(2)] center dot 2CH(2)Cl(2), and [Cu(hfac)(2)L(2)Cu(2)Piv(4)] center dot 3C(7)H(8) (where acac is acetylacetonate and Piv is trimethylacetate), or free L), the effect vanished when the packing changed.
• Cyclic voltammetry of nitronyl- and iminonitroxyls detected by electron spin resonance
  作者：M. K. Kadirov、E. V. Tret’yakov、Yu. G. Budnikova、K. V. Kholin、M. I. Valitov、V. N. Vavilova、V. I. Ovcharenko、R. Z. Sagdeev、O. G. Sinyashin

  DOI：10.1134/s0036024409120280

  日期：2009.1

  The combined cyclic voltammetry method (cyclic voltammetry detected by electron spin resonance, CVA-DESR CVA) was applied to study the electrochemical reactions of nitronyl- and iminonitroxyls (NN and IN) and to estimate the diffusion and absorption characteristics of their products. The ESR method yielded the hyperfine structure constants, including C-13. Even if exposed to lower temperature, all the studied NN were shown to spontaneously lose oxygen and to convert gradually into the relevant IN. For each specific NN, the combined CVA-DESR CVA experiments found the reduction potential value at which it can be virtually completely converted into the relevant IN.
• Crystals of the CuII complex with nitronyl nitroxide and imino nitroxide exhibiting mechanical activity
  作者：E. V. Tretyakov、S. V. Fokin、E. Yu. Fursova、O. V. Kuznetsova、G. V. Romanenko、R. Z. Sagdeev、V. I. Ovcharenko

  DOI：10.1007/s11172-013-0260-5

  日期：2013.8

  As part of continuing studies of multispin compounds capable of exhibiting chemomechanical activity, a series of heterospin solids of the composition [Cu(hfac)2L x L′2−x ], [Cu(hfac)2L′], [Cu2(Piv)4L′2]·0.5C6H14, and [Cu2(hfac)2(Piv)2L′2], where hfac is the hexafluoroacetylacetonate anion, L is 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, L′ is the imino nitroxide analog of L, viz., 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-1-oxyl, and Piv is the 2,2-dimethylpropionate anion, were synthesized and characterized. The packing of the synthesized crystals of the solid solutions [Cu(hfac)2L x L′2-x ], where L predominates, is similar to that for [Cu(hfac)2L2], and these crystals are able to undergo chemomechanical motion. On the contrary, the crystals of [Cu(hfac)2L x L′2−x ], where L′ predominates, have structural parameters similar to those of [Cu(hfac)2L′2] and do not exhibit thermally activated or photoactivated chemomechanical activity.

  作为能够表现出化学机械活性的多自旋化合物持续研究的一部分，一系列组成为 [Cu(hfac)2L x L'2−x ]、[Cu(hfac)2L']、[Cu2(Piv) 的异质自旋固体4L'2]·0.5C6H14 和 [Cu2(hfac)2(Piv)2L'2]，其中 hfac 是六氟乙酰丙酮阴离子，L 是 4,4,5,5-四甲基-2-(1-甲基-1H) -咪唑-5-基)-4,5-二氢-1H-咪唑-3-氧化物-1-氧基，L'是L的亚氨基硝基氧类似物，即4,4,5,5-四甲基-2合成并表征了-(1-甲基-1H-咪唑-5-基)-4,5-二氢-1H-咪唑-1-氧基，Piv是2,2-二甲基丙酸根阴离子。固溶体 [Cu(hfac)2L x L'2-x ] 的合成晶体的堆积（其中 L 占主导地位）与 [Cu(hfac)2L2] 的堆积类似，并且这些晶体能够进行化学机械运动。相反，[Cu(hfac)2L x L'2−x ]晶体（其中L'占主导地位）具有与[Cu(hfac)2L'2]相似的结构参数，并且不表现出热激活或光激活化学机械活动。