2,6-bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl-1-oxyl)pyridine | 155504-89-5

• 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: 2,6-bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl-1-oxyl)pyridine
• 英文别名: 2,6-bis(1'-oxyl-4',4',5',5'-tetra-methylimidazolin-2'-yl)pyridine；2,6-bis{1-oxyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl}pyridine；2,6-bis(4',4',5',5'-tetramethyl-4',5'-dihydro-1'H-imidazol-1'-oxyl-2'-yl)pyridine；Bisimpy；4,4,5,5-Tetramethyl-2-[6-(4,4,5,5-tetramethyl-1-oxidoimidazol-2-yl)pyridin-2-yl]imidazol-1-ium 1-oxide
• CAS: 155504-89-5
• 化学式: C₁₉H₂₇N₅O₂
• 分子量: 357.456
• InChiKey: HURDHRCKPXCZNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  84
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,6-bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl-1-oxyl)pyridine 、 zinc(II) chloride 以 乙醇 为溶剂， 生成 [2,6-bis(1'-oxyl-4',4',5',5'-tetramethyl-4',5'-dihydro-1'H-imidazol-2'-yl)pyridine]zinc(II) dichloride
  参考文献：
  名称：

  Experimental and Theoretical Studies on Ferromagnetically Coupled Metal Complexes with Imino Nitroxides

  摘要：

  Copper(II), zinc(II), and nickel(II) complexes with tridentate imino nitroxyl diradicals, [CuCl(bisimpy)(MeOH)]-(PF6) (1), [ZnCl2(bisimpy)] (2), and [NiCl(bisimpy)(H2O)(2)]Cl . 2H(2)O (3) (bisimpy = 2,6-bis(1'-oxyl-4',4',5',5'-tetramethyl-4',5'-dihydro-1'H-imidazol-2'-yl)pyridine), were prepared, and their magnetic properties were studied. In 1, the Cu(II) ion has a square pyramidal coordination geometry, of which the equatorial coordination sites are occupied by three nitrogen atoms from the bisimpy and a chloride ion. The coordination geometry of the Zn(II) ion in 2 can be described as a trigonal bipyramid, with two chloride ions and a bisimpy. In 3, the Ni(II) ion has a distorted octahedral coordination geometry, of which four coordination sites are coordinated by the bisimpy and chloride ion, and two water molecules occupy the remaining cis positions. Magnetic susceptibility and EPR measurements revealed that in 1 and 3 the Cu(II) and Ni(II) ions with imino nitroxyl diraicals were ferromagnetically respectively, and the coupled, with the coupling constants J (H = -2J(ij)SigmaS(i)S(j)) of +165(1) and 109(2) cm(-1), intraligand ferromagnetic interactions in 1-3 were very weak. DFT molecular orbital calculations were performed on the diradical ligand, 1, and 2 to study the spin density distribution before and after coordination to the metal ions.

  DOI：

  10.1021/ic0102384
• 作为产物：
  描述：

  NITPymbis 在 溶剂黄146 、 sodium nitrite 作用下， 以 氯仿 、 水 为溶剂， 反应 1.0h， 以38%的产率得到2,6-bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl-1-oxyl)pyridine
  参考文献：
  名称：

  基于2,6-吡啶基取代的硝酰基和亚氨基亚硝基基团的五种Mn（II）和Co（II）配合物的合成，结构和磁性表征

  摘要：

  摘要双自由基2,6-NITpy（1）（2,6-NITpy = 2,6-bis（3'-oxide-1'-oxyl-4'，4'，5'，5'-tetramethylimidazolin- 2'-基）吡啶），2-NIT-6-IMpy（2）（2-NIT-6-IMpy = 2-（3'-氧化物-1'-氧基-4'，4'，5'，5 '-四甲基咪唑啉-2'-基）-6-（1'-氧基-4'，4'，5'，5'-四甲基咪唑啉-2'-基）吡啶）或2,6-IMpy（3 ）（2,6-IMpy = 2,6-双（1'-氧基-4'，4'，5'，5'-四甲基咪唑啉-2'-基）吡啶）与M（hfac）2·XH2O （M ＝ MnII，CoII）进行了研究。发现这些反应与所用金属离子的类型有关。有趣的是，氧化还原反应参与了配合物的合成过程。通过X射线分析阐明了五种配合物的结构，并详细研究了它们的磁性。高温范围内所有五个络合物的χMT的温

  DOI：

  10.1016/j.ica.2016.01.037

文献信息

• Selective synthesis of a novel family of oligopyridine based imino-nitroxide biradicals catalysed by selenium dioxide
  作者：Gilles Ulrich、Raymond Ziessel

  DOI：10.1016/0040-4039(94)88027-1

  日期：1994.2

  8-naphthyridine from the corresponding dialdehydes and N,N′-dihydroxy-2,3-diamino-2,3-dimethylbutane in the presence of catalytic amounts of SeO2. Mild oxidation afforded the corresponding stable imino-nitroxide biradicals 4 to 11.

  由吡啶，2,2'-联吡啶，1,10-菲咯啉，哒嗪和1,8-萘啶基于相应的二醛和N，N'-二羟基-2,3-二氨基-选择性合成双-N-羟基咪唑烷2,3-二甲基丁烷在催化量的SeO 2的存在下。轻度氧化得到相应的稳定的亚氨基硝基氧双自由基4至11。
• Modulating the Magnetic Properties of Copper(II)/Nitroxyl Heterospin Complexes by Suppression of the Jahn–Teller Distortion
  作者：Sam Greatorex、Sergey V. Fokin、Rafal Kulmaczewski、Mihoko Yamada、Oscar Cespedes、Nobuto Yoshinari、Takumi Konno、Stephen Sproules、Victor I. Ovcharenko、Malcolm A. Halcrow

  DOI：10.1021/acs.inorgchem.0c01345

  日期：2020.7.6

  [Cu(L)L1][BF4]2 (L1 = 2,6-bis1-oxyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl}pyridine) complexes are reported. Ferromagnetic coupling between the Cu and L1 ligand spins is enhanced by an L coligand with distal methyl substituents, which is attributed to a sterically induced suppression of its Jahn–Teller distortion.

  一系列六坐标的[Cu（L）L 1 ] [BF 4 ] 2（L 1 = 2,6-双1-氧基-4,4,5,5-四甲基-4,5-二氢-1报道了H-咪唑-2-基}吡啶）配合物。带有末端甲基取代基的大肠菌素增强了Cu和L 1配体自旋之间的铁磁耦合，这归因于空间诱导的Jahn-Teller畸变抑制。
• Spin Canting in a Cobalt(II) Radical Complex with an Acentric Counter Anion
  作者：Kiyotaka Mitsumoto、Takuya Shiga、Motohiro Nakano、Masayuki Nihei、Hiroyuki Nishikawa、Hiroki Oshio

  DOI：10.1002/ejic.200800824

  日期：2008.11

  Cobalt(II) radical complexes with centric and acentric counter anions, [CoCl(bisimpy)(MeOH)2]X [bisimpy = 2,6-bis(4′,4′,5′,5′-tetramethyl-4′,5′-dihydro-1′H-imidazol-1′-oxyl-2′-yl)pyridine; X = PF6 (1), and ClO4 (2)], crystallize in the centrosymmetric and polar space groups, respectively. Compound 1 is paramagnetic, whereas spin canting in 2 leads to a metamagnetic transition with a critical field

  钴 (II) 自由基与中心和非中心抗衡阴离子复合，[CoCl(bisimpy)(MeOH)2]X [bisimpy = 2,6-bis(4',4',5',5'-tetramethyl-4', 5'-二氢-1'H-咪唑-1'-氧基-2'-基)吡啶；X = PF6 (1) 和 ClO4 (2)]，分别在中心对称和极性空间群中结晶。化合物 1 是顺磁性的，而化合物 2 的自旋倾斜导致在 1.8 K 下临界场为 1300 Oe 的超磁跃迁。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• A One-Dimensional Helical Copper(II) Imino Nitroxide
  作者：Hiroki Oshio、Takashi Watanabe、Akihiro Ohto、Tasuku Ito

  DOI：10.1021/ic960938m

  日期：1997.4.1

  reaction of [Cu(I)(CH(3)CN)(4)](PF(6)) with a biradical of imino nitroxide in methanol yielded a copper(II) complex [Cu(II)(imapy)](PF6) (2) (Himapy = 2-(1'-oxy-4',4',5',5'-tetramethyl-4',5'-dihydro-1'H-imidazol-2'-yl)-6-(1"-oxyl-4",4",5",5"-tetramethyl-4",5"-dihydro-1"H-imidazol-2"-yl)pyridine)). In 2 one of the nitroxides in the ligand was reduced to a hydroxyamino anion and the Cu(I) ion was oxidized

  其中一个配位氧原子来自下一个分子中的羟氨基 Cu（II）离子被亚氨基-羟基氨基阴离子桥接以形成一维结构，每个Cu（II）离子具有配位的亚氨基硝基氧化物。复杂分子位于4倍螺旋轴上，这导致亚氨基亚硝酸盐的逆时针螺旋排列。磁化率测量表明，反铁磁相互作用是有效的。该系统被视为Cu（II）自由基物种的一维链，链内和Cu（II）自由基相互作用的耦合常数J（1）和J（2）估计为-6和-23 cm（-）（1）。Cu（II）离子被亚氨基-羟基氨基阴离子桥接以形成一维结构，每个Cu（II）离子具有配位的亚氨基硝基氧化物。复杂分子位于4倍螺旋轴上，这导致亚氨基亚硝酸盐的逆时针螺旋排列。磁化率测量表明，反铁磁相互作用是有效的。该系统被视为Cu（II）自由基物种的一维链，链内和Cu（II）自由基相互作用的耦合常数J（1）和J（2）估计为-6和-23 cm（-）（1）。Cu（II）离子被亚氨基-羟基氨基阴离子桥接以形
• Oshio, Hiroki; Yamamoto, Masashi; Ito, Tasuku, Journal of the Chemical Society, Dalton Transactions, 1999, p. 2641 - 2644
  作者：Oshio, Hiroki、Yamamoto, Masashi、Ito, Tasuku

  DOI：——

  日期：——