1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis-(dimethylamino)benzene | 1413265-62-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis-(dimethylamino)benzene
• 英文别名: 4,5-bis(dimethylamino)benzene-1,2-bis(3,5-di-tert-butylsalicylimine)；2,4-Ditert-butyl-6-[[2-[(3,5-ditert-butyl-2-hydroxyphenyl)methylideneamino]-4,5-bis(dimethylamino)phenyl]iminomethyl]phenol
• CAS: 1413265-62-9
• 化学式: C₄₀H₅₈N₄O₂
• 分子量: 626.926
• InChiKey: AQRAPTPSYFKUHZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  46
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  71.7
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis-(dimethylamino)benzene 、 nickel(II) acetate tetrahydrate 以 甲醇 为溶剂， 反应 1.0h， 以96%的产率得到[Ni(4,5-bis(dimethylamino)benzene-1,2-bis(3,5-di-tert-butylsalicylimine)(-2H))]
  参考文献：
  名称：

  Reversible Double Oxidation and Protonation of the Non-Innocent Bridge in a Nickel(II) Salophen Complex

  摘要：

  Substitution on the aromatic bridge of a nickel(II) salophen complex with electron-donating dimethylamino substituents creates a ligand with three stable, easily and reversibly accessible oxidation states. The one-electron-oxidized product is characterized as a nickel(II) radical complex with the radical bore by the central substituted aromatic ring, in contrast to other nickel(II) salen or salophen complexes that oxidize on the phenolate moieties. The doubly oxidized product, a singlet species, is best described as having an iminobenzoquinone bridge with a vinylogous distribution of bond lengths between the dimethylamino substituents. Protonation of the dimethylamino substituents inhibits these redox processes on the time scale of cyclovoltammetry, but electrolysis and chemical oxidation are consistent with deprotonation occurring concomitantly with electron transfer to yield the mono- and dioxidized species described above.

  DOI：

  10.1021/ic301684h
• 作为产物：
  描述：

  4,5-bis(dimethylamino)-1,2-dinitrobenzene 在 palladium 10% on activated carbon 、 氢气 、 原甲酸三甲酯 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis-(dimethylamino)benzene
  参考文献：
  名称：

  Reversible Double Oxidation and Protonation of the Non-Innocent Bridge in a Nickel(II) Salophen Complex

  摘要：

  Substitution on the aromatic bridge of a nickel(II) salophen complex with electron-donating dimethylamino substituents creates a ligand with three stable, easily and reversibly accessible oxidation states. The one-electron-oxidized product is characterized as a nickel(II) radical complex with the radical bore by the central substituted aromatic ring, in contrast to other nickel(II) salen or salophen complexes that oxidize on the phenolate moieties. The doubly oxidized product, a singlet species, is best described as having an iminobenzoquinone bridge with a vinylogous distribution of bond lengths between the dimethylamino substituents. Protonation of the dimethylamino substituents inhibits these redox processes on the time scale of cyclovoltammetry, but electrolysis and chemical oxidation are consistent with deprotonation occurring concomitantly with electron transfer to yield the mono- and dioxidized species described above.

  DOI：

  10.1021/ic301684h

文献信息

• Redox Noninnocence of the Bridge in Copper(II) Salophen and Bis(oxamato) Complexes
  作者：David de Bellefeuille、Maylis Orio、Anne-Laure Barra、Ally Aukauloo、Yves Journaux、Christian Philouze、Xavier Ottenwaelder、Fabrice Thomas

  DOI：10.1021/acs.inorgchem.5b01285

  日期：2015.9.21

  absorptions, which are diagnostic of π radicals. They display a triplet signal in their electron paramagnetic resonance spectra, which stem from magnetic coupling between the ligand-radical spin and the copper(II) spin. The zero-field-splitting parameters are larger for 2– than 1+ because of greater delocalization of the spin density onto the coordinated amidato N atoms. Density functional theory calculations

  1,2-双（2-羟基-3,5-二叔丁基苯甲基氨基）-4,5-双（二甲基氨基）苯（1）和N- [4,5制备了双（二甲基氨基）-2-（草酰氨基）苯]草酸酯（2 2–）。报导了配体H 2 L 1和Et 2 H 2 L 2的晶体结构以及相应的配合物。配体各自显示单电子氧化波，其被分配为将双（二甲基氨基）苯部分氧化成π基团。1号和2号复合物2–表现出可逆的单电子氧化波在它们的循环伏安图（Ë 1/2 1 = 0.14和ë 1/2 2 = 0.31 V代表1和Ë 1/2 1 = -0.47相对于Fc + / Fc的为2 2-）。第一过程对应于双（二甲基氨基）苯中心环的氧化成π基团，而用于第二过程1被归因于π基团为α-diiminoquinone的氧化。单电子氧化的物质1 +和2 –表现出强烈的可见光-近红外吸收，可诊断π自由基。它们在电子顺磁共振波谱中显示三重态信号，该信号来自配体自由基自旋和铜（II）自旋之间的磁耦合。零场分裂参数对于2