N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine | 2951-81-7

• 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: N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine
• 英文别名: N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine；1,3-bis(4,6-di-tert-butyl-2-iminophenol)benzene；6,6'-(1,3-Phenylenebis(azanediyl))bis(2,4-di-tert-butylphenol)；2,4-ditert-butyl-6-[3-(3,5-ditert-butyl-2-hydroxyanilino)anilino]phenol
• CAS: 2951-81-7
• 化学式: C₃₄H₄₈N₂O₂
• 分子量: 516.767
• InChiKey: IMFCDEPWGKWRMH-UHFFFAOYSA-N

物化性质

• 熔点：
  241-241.5 °C
• 沸点：
  549.7±50.0 °C(Predicted)
• 密度：
  1.065±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  64.5
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine 、 iron(II) chloride 在 triethylamine 作用下， 以 乙腈 为溶剂， 生成 Fe2(N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine(2-))3
  参考文献：
  名称：

  Bonding Coordination Requirements Induce Antiferromagnetic Coupling between m-Phenylene Bridged o-Iminosemiquinonato Diradicals

  摘要：

  Triply bridged bis-iminodioxolene dinuclear metal complexes of general formula M-2(diox-diox)(3), with M = Co, Fe, have been synthesized using the bis-bidentate ligand N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine. These complexes were characterized by means of X-ray, HF-EPR, and magnetic measurements. X-ray structures clearly show that both complexes can be described as containing three bis-iminosemiquinonato ligands acting in a bis-bidentate manner toward tripositive metal ions. The magnetic data show that both of these complexes have singlet ground states. The observed experimental behavior indicates the existence of intraligand antiferromagnetic interactions between the three pairs of m-phenylene units linked iminosemiquinonato radicals (J = 21 cm(-1) for the cobalt complex and J = 11 cm(-1) for the iron one). It is here suggested that the conditions for the ferromagnetic coupling that is expected to characterize the free diradical ligand are no longer satisfied because of the severe torsional distortion induced by the metal coordination.

  DOI：

  10.1021/ic026160o
• 作为产物：
  描述：

  3,5-二叔丁基邻苯二酚 、 间苯二胺 在 三乙胺 作用下， 以 正庚烷 为溶剂， 反应 48.0h， 以96%的产率得到N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine
  参考文献：
  名称：

  双核和单核锰（IV）-自由基配合物及其催化儿茶酚酶活性。

  摘要：

  描述了基于苯胺和间苯二胺的七个邻氨基苯酚配体，分别作为单核和双核非纯配体，以及它们的七个Mn（IV）配合物1-7。其中1个为双核，2-7个为单核，其中的配体以其氧化的邻亚氨基苯并半醌基形式被配位。通过X射线衍射确定1和3的晶体结构，并通过各种物理方法（包括EPR和可变温度（2-290 K）磁化率测量）建立电子结构。电化学测量（CV和SQW）主要表明以配体为中心的氧化还原过程。Mn（IV）-自由基配合物1-7以分子氧作为唯一氧化剂催化3,5-二叔丁基邻苯二酚的氧化，得到3，5-二叔丁基醌在温和的条件下定量地模拟含铜酶儿茶酚氧化酶的功能。提出了一种自由基的“开-关”机理，该氧化自由基没有金属中心的氧化还原参与。发现配合物1是受阻酚与二苯并醌的氧化CC偶联的良好催化剂。

  DOI：

  10.1039/b410842f

文献信息

• Dinuclear Iron(III) and Cobalt(III) Complexes Featuring a Biradical Bridge: Their Molecular Structures and Magnetic, Spectroscopic, and Redox Properties
  作者：Dhrubajyoti Mondal、Mithun Chandra Majee、Sanchita Kundu、Max Mörtel、Ghulam Abbas、Akira Endo、Marat M. Khusniyarov、Muktimoy Chaudhury

  DOI：10.1021/acs.inorgchem.7b02340

  日期：2018.2.5

  units was used to synthesize novel binuclear complexes [(LR)MIII(•LB•)MIII(LR)](ClO4)2, M = Fe (1) and Co (2, 3), with HLR (R = CH3, Cl) being the facially coordinating tetradentate coligands. Upon the synthesis, the fully reduced amidophenolate form of the ligand (LB)4– becomes oxidized, resulting in the formation of a rare example of a biradical (•LB•)2– bridge connecting two metal ions, as supported

  使用具有两个邻氨基苯酚非清纯单元的双双配体H 4 L B来合成新型双核络合物[（L R）M III（•L B •）M III（L R）]（ClO 4）2，M =的Fe（1）和Co（2，3）中，用HL - [R（R = CH 3，Cl）的作为表面式地协调四齿共配体。合成后，完全还原的酰胺基苯酚配体形式（L B）4–会被氧化，导致形成X射线晶体学支持的连接两个金属离子的双自由基（•L B •）2–桥的罕见例子。配合物的电子结构已通过Mössbauer光谱，磁化率测量和电子顺磁共振（EPR）光谱进行了探测。物种1包含两个高自旋的Fe（III）离子（小号= 5/2），每个耦合强反铁磁（| Ĵ |>150厘米-1 ; H ^ = - 2J S ^ 1 S ^ 2）配有一个半醌的π基团（小号= 1/2）桥接形式（•L B•）2 –配体。每个[Fe（III）+ R ● ]单体单元的有效S = 2自旋，然后与J
• A unique series of dinuclear transition metal–polyradical complexes with a m-phenylenediamine spacer and their catalytic reactivity
  作者：Soumen Mukherjee、Eva Rentschler、Thomas Weyhermüller、Karl Wieghardt、Phalguni Chaudhuri

  DOI：10.1039/b300792h

  日期：——

  A series of dinuclear transition metal complexes with either six or four iminosemiquinone radicals, in which the metal centres are separated by a distance of ∼6.8 Å, together with their catalytic reactivity is reported.

  报告了一系列含有六个或四个亚氨基喹啉酮自由基的双核过渡金属配合物及其催化反应性。
• Dinuclear ruthenium bipyridine complexes with a bis(iminodioxolene)-meta-phenylene ligand: magnetic coupling and mixed valence character of the semiquinonato species
  作者：Fabrizia Fabrizi De Biani、Andrea Dei、Claudio Sangregorio、Lorenzo Sorace

  DOI：10.1039/b508401f

  日期：——

  strong ferromagnetic interaction (H=JS(1) x S(2), J=-85(5) cm(-1)). This result is the theoretically expected one and it is contrasting with the antiferromagnetic interaction observed in previously investigated complexes containing the same ligand. It is suggested that the different behaviour is determined by the different coordination requirements occurring in these complexes. The spectroelectrochemical

  双核双亚氨基半醌[Ru（bpy）（2）（L）（2）Ru（bpy）（2）]（PF（6））（2）络合物，其中L是N，N'-bis的去质子化形式（3,5-二叔丁基-2-羟苯基）-1,3-苯二胺（H（4）L）已经合成。为了比较，还研究了由N-苯基-邻氨基苯酚（H（2）L'）形成的单核亚氨基半醌[Ru（bpy）（2）L'] PF（6）。磁性研究表明，bis-semiquinonato物种具有中等强度的铁磁相互作用（H = JS（1）x S（2），J = -85（5）cm（-1））。该结果是理论上预期的结果，并且与先前研究的含有相同配体的复合物中观察到的反铁磁相互作用形成对比。建议不同的行为是由这些复合物中发生的不同协调要求决定的。光谱电化学分析清楚地证明了配体的单-半喹诺酮形式的化合价。包含喹诺酮-半喹诺酮和半喹诺酮-邻苯二酚桥联配体的两种混合价半喹诺酮物质可描述为II类，但显示出显着不同的电子偶联。讨论了决定这种行为的电子因素。
• HF-EPR to monitor electron transfer in mixed valence dioxolene metal complexes
  作者：Andrea Dei、Dante Gatteschi、Claudio Sangregorio、Lorenzo Sorace、Maria G.F. Vaz

  DOI：10.1016/s0009-2614(02)01831-6

  日期：2003.1

  The reaction of Mn(II) salts with N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine yields a dinuclear Mn2L3 complex, which on the basis of its structural and magnetic characterisation can be formulated as a Mn(IV) derivative of both dinegative bis-iminosemiquinonato and mixed valence trinegative iminosemiquinonato-iminocatecholato forms of the reacting ligand. HF-EPR spectra at various frequencies suggest that the electron transfer process in this mixed valence species is frozen on the time scale of EPR at high frequency, whereas is still dynamic at lower frequencies. This spectral behaviour therefore indicates a thermally activated character of the electron transfer process, as expected in a class 11 mixed valence system. (C) 2002 Elsevier Science B.V. All rights reserved.