bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis[4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl]nickel(II) | 1259289-37-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis[4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl]nickel(II)
• 英文别名: bis(hexafluoroacetylacetonato)bis[4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide]nickel(II)
• CAS: 1259289-37-6
• 化学式: C₃₂H₃₆F₁₂N₈NiO₈
• 分子量: 947.357
• InChiKey: BBXNAAZIERNLGC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis[4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl]nickel(II) 以 neat (no solvent, solid phase) 为溶剂， 生成 [Ni(II)(hexafluoroacetylacetonate)2(4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-1-oxyl)2]
  参考文献：
  名称：

  “Jumping Crystals”: Oxygen-Evolving Metal-Nitroxide Complexes

  摘要：

  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.

  DOI：

  10.1021/ic1022483
• 作为产物：
  描述：

  [Ni(II)(1,1,1,5,5,5-hexafluoroacetylacetonate)₂]*2H₂O 、 2-(1-methylimidazol-5-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole 3-oxide-1-oxyl 以 二氯甲烷 、 甲苯 为溶剂， 反应 24.0h， 以38%的产率得到bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)bis[4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl]nickel(II)
  参考文献：
  名称：

  “跳跃”晶体：CuII 配合物与 N-甲基咪唑基和 N-甲基三唑基取代的硝酰基氮氧化物的结构和性质

  摘要：

  摘要 为寻找有利于异旋晶体出现化学机械活性的因素，合成并表征了一系列新型异旋配合物。它包括[Cu(tfac)2LIm2]·2CH2Cl2、[Cu(tfac)2LIm2]·2EtOH、[[Cu(pfu)2]2LIm3]·1/2CH2Cl2、[Cu(pfh)2LIm2]·1/2CH2Cl2、[ Cu(piv)2LIm2]·2MeOH, [Co(piv)2LIm2], [$$ Cu(hfac)_2 L^{CD_3 } _2 $$], [Cu(hfac)2LTr]2·CH2Cl2, 和 [Cu( hfac)2LTr2] (LIm, $$ L^{CD_3 } $$, 和 LTr 分别是 N-甲基咪唑基-、N-三甲基咪唑基-和 N-甲基三唑基-取代的硝酰基氮氧化物；tfac、hfac、pfu、pfh 和piv 是带电的配位抗磁性配体 1,1,5,5-四氟戊烷-2,4-二酸，1,1,1,5,5,5-六氟戊烷-2

  DOI：

  10.1007/s11172-011-0381-7

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。