Ni(2+)-α,β,γ,δ-tetra(4-methoxyphenyl)porphine | 39828-57-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Ni(2+)-α,β,γ,δ-tetra(4-methoxyphenyl)porphine
• 英文别名: nickel 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin；meso-tetrakis(4-methoxyphenyl)porphyrin nickel(II)；nickel-5,10,15,20-tetra(4-methoxyphenyl)porphyrin
• CAS: 39828-57-4
• 化学式: C₄₈H₃₆N₄NiO₄
• 分子量: 791.528
• InChiKey: WIHHBQHMISDZOC-NHZJRHMYSA-N

物化性质

• 熔点：
  275.75 °C

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：

  Ni(2+)-α,β,γ,δ-tetra(4-methoxyphenyl)porphine 以 neat (no solvent) 为溶剂， 生成 nickel(II) oxide
  参考文献：
  名称：

  Thermal analysis study of 5,10,15,20-tetrakis (methoxyphenyl) porphyrins and their nickel complexes

  摘要：

  The thermal stability in air of 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin (4-TMPP), 5,10,15,20-tetrakis (3-methoxyphenyl) porphyrin (3-TMPP), and their nickel metallo-complexes (4-TMPP-Ni and 3-TMPP-Ni) has been investigated by thermogravimetry (TG). 4-TMPP and 4-TMPP-Ni exhibit higher thermal stability compared to 3-TMPP and 3-TMPP-Ni. Nickel complexes exhibit a little higher thermal stability than the corresponding porphyrins. The thermal behavior including melting temperature and enthalpy of fusion was determined by differential scanning calorimetry (DSC) and infrared spectra (IR). The activation energies of thermal decompositions of 4-TMPP-Ni and 3-TMPP-Ni were obtained by integral model-free method; the mechanism functions and pre-exponential factors were determined by master plots method. The kinetic models follow the same mechanism function, Avramie-Erofeev equations with integral forms g(alpha)=[-ln (1-alpha)](0.278) and g(alpha)=[-ln (1-alpha)](0.260), respectively. (C) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.tca.2005.10.017
• 作为产物：
  描述：

  bis(acetylacetonate)nickel(II) 、 5,10,15,20-tetrakis(4-methoxyphenyl)-21,22-dihydroporphyrin 以 氯仿 为溶剂， 生成 Ni(2+)-α,β,γ,δ-tetra(4-methoxyphenyl)porphine
  参考文献：
  名称：

  通过 Ni-N-C 和封装的 Ni 纳米粒子之间的协同作用，高选择性 CO2 电还原为 CO

  摘要：

  选择性电化学 CO 2还原反应 (CO 2 RR)非常需要高效催化剂。Ni 单原子催化剂被认为是有前途的 CO 2 RR 催化剂，而 Ni NPs 有望催化竞争性 HER。在这项工作中，我们通过将 Ni NPs 封装到多孔 Ni-N-C 纳米片 (Ni@Ni-N-C) 中来对其进行修饰，以增强 Ni NPs 和分散的 Ni-N 物种之间对 CO 2 RR 的协同作用。CO 法拉第效率 (FE CO ) 在 -0.9 V 时达到 96.4%，并在宽电位窗口内保持超过 90%。更重要的是，从 −50 到 −170 mA cm -2获得了超过 94% 的 FE CO值，峰值 FE CO流通池中 99%。我们的工作表明，Ni NPs 的表面改性可以抑制意外的 HER 并激活表面位点，为 CO 2 RR 催化剂提供实用的设计策略。

  DOI：

  10.1039/d2dt03680k

文献信息

• One-pot general synthesis of metalloporphyrins
  作者：Anil Kumar、Suman Maji、Prashant Dubey、G.J. Abhilash、Sohini Pandey、Sabyasachi Sarkar

  DOI：10.1016/j.tetlet.2007.08.046

  日期：2007.10

  A new general one-pot method for the synthesis of various metalloporphyrins has been developed from pyrrole and substituted aldehydes using transition metal salts. This method allows higher working concentrations than those previously reported. Along with the reported metalloporphyrins, some new metalloporphyrins were synthesized in good yield.

  已经开发了一种新的通用一锅法，该方法可使用吡咯和取代醛，使用过渡金属盐合成各种金属卟啉。这种方法比以前报道的允许更高的工作浓度。与报道的金属卟啉一起，以高收率合成了一些新的金属卟啉。
• Insertion of Ni(I) into Porphyrins at Room Temperature: Preparation of Ni(II)porphyrins, and Ni(II)chlorins and Observation of Hydroporphyrin Intermediates
  作者：Morten K. Peters、Rainer Herges

  DOI：10.1021/acs.inorgchem.7b03164

  日期：2018.3.19

  enzymatic cofactors in the global carbon cycle (cofactor F430), and as powerful catalysts in solar-to-fuel-processes such as the hydrogen evolution reaction, and the reduction of CO and CO2. The preparation of Ni(II)porphyrins requires harsh conditions, and characterization of the reduced species is intricate. We present a very mild, convenient, and high yielding method of inserting Ni into electron

  还原的镍卟啉在全球碳循环中作为酶促辅助因子（辅助因子F430）起着重要的作用，并且在太阳能转化为燃料的过程（例如氢释放反应以及CO和CO 2的还原）中起着重要的催化剂的作用。Ni（II）卟啉的制备需要苛刻的条件，并且还原物种的表征十分复杂。我们提出了一种非常温和，方便且高产的方法，将Ni插入富电子和缺电子的卟啉中，同时可以使用Ni（II）phlorins和Ni（II）chlorins和Ni（II）卟啉。
• Synthesis and Versatile Reactions of β-Azidotetraarylporphyrins
  作者：Dong-Mei Shen、Chao Liu、Qing-Yun Chen

  DOI：10.1002/ejoc.200601046

  日期：2007.3

  A variety of β-azidotetraarylporphyrins were conveniently synthesized by classical conversion of the amino groups of β-aminotetraarylporphyrins into azido groups through diazotization and subsequent treatment with sodium azide. Their thermal reaction and CuI-catalyzed 1,3-dipolar cycloaddition with various alkynes were also reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  通过重氮化和随后用叠氮化钠处理将 β-氨基四芳基卟啉的氨基经典转化为叠氮基，可以方便地合成多种 β-叠氮四芳基卟啉。还报道了它们的热反应和 CuI 催化的 1,3-偶极环加成与各种炔烃。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Formylation Reaction in Series of meso-Tetraaryl Substituted Porphyrins and Chlorins
  作者：A. F. Mironov、T. V. Moskalchuk、A. S. Shashkov

  DOI：10.1023/b:rubi.0000030133.22914.8c

  日期：2004.5

  The formylation of nickel complexes of meso-tetraaryl substituted porphyrins and chlorins was studied. An obvious regioselectivity was observed for the introduction of the first and subsequent formyl groups into chlorins.

  研究了内消旋四芳基取代的卟啉和二氢卟酚的镍配合物的甲酰化。对于将第一个和随后的甲酰基引入二氢卟酚中，观察到明显的区域选择性。
• Hydrocarbon Oxidation by a Porphyrin‐π‐Cation Radical Complex
  作者：Marta Lovisari、Oscar Reid Kelly、Aidan R. McDonald

  DOI：10.1002/anie.202303083

  日期：2023.8

  A π-cation radical complex without ancillary proton accepting ligand/groups was found to perform oxidative C−H bond activation, yielding hydroxylated substrates in the presence of air. According to kinetic studies, the nickel porphyrin-π-cation radical accepted an electron to oxidise substrates through a concerted PCET mechanism.

  没有辅助质子接受配体/基团的 π-阳离子自由基复合物被发现可以进行氧化 C-H 键活化，在空气存在下产生羟基化底物。根据动力学研究，镍卟啉-π-阳离子自由基接受电子，通过协调的PCET机制氧化底物。