[5,10,15,20-tetra(p-nitro)phenylporphyrin]cobalt(II) | 52242-05-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: [5,10,15,20-tetra(p-nitro)phenylporphyrin]cobalt(II)
• 英文别名: tetrakis(4-nitrophenyl)porphyrin cobalt；CoTNPP；5,10,15,20-tetrakis(4-nitrophenyl)porphin cobalt；cobalt(II) meso-tetra(p-nitro)phenylporphyrin；[Co(II)(tetra(4-nitrophenyl)porphyrin)]
• CAS: 52242-05-4
• 化学式: C₄₄H₂₄CoN₈O₈
• 分子量: 851.717
• InChiKey: CZSSALWCANXRQT-DAJBKUBHSA-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：

  [5,10,15,20-tetra(p-nitro)phenylporphyrin]cobalt(II) 、 氧化亚氮 在 哌啶 作用下， 以 二氯甲烷 为溶剂， 以50%的产率得到nitrolsylcobalt(II) meso-tetra(p-nitrophenyl)porphyrin
  参考文献：
  名称：

  Photochemistry of Nitrosyl Metalloporphyrins:  Mechanisms of the Photoinduced Release and Recombination of NO

  摘要：

  A series of substituted nitrosylmetalloporphyrins of the type M(NO)(meso-tetra(p-X)phenylporphyrin) (M Co, Mn; X = H, NO2, OMe) were prepared and studied by laser flash photolysis. The kinetics of the recombination reactions between the metalloporphyrins and NO in THF were examined. The recombination mechanism appears to be more complicated than the simple second-order process previously reported. Out-of-plane puckering of the porphyrin ring immediately after denitrosylation is one possible explanation. Kinetic experiments and NO transfer studies between manganese and cobalt porphyrins suggest that these compounds exist in equilibrium with NO in solution. Varying the substituents in the phenyl ring of the tetraphenylporphyrin ligand has little effect on rates of recombination with NO.

  DOI：

  10.1021/jp9811169
• 作为产物：
  描述：

  cobalt(II) chloride 、 meso-tetrakis(4-nitrophenyl)porphyrin 以 N,N-二甲基甲酰胺 为溶剂， 以11%的产率得到[5,10,15,20-tetra(p-nitro)phenylporphyrin]cobalt(II)
  参考文献：
  名称：

  Synthesis of 5,10,15,20-Tetrakisphenylporphins on a Carbon Support for the Cathodic Reduction of Oxygen in Fuel Cells

  摘要：

  AbstractSeveral substituted Fe‐ and Co‐containing tetraphenylporphins 1 were loaded on carbon either by adsorption from acetone or by in situ synthesis on the carbon support. The porphin/carbon combinations were pyrolyzed at 800°C. The electrocatalytic activities in the reduction of dioxygen were investigated in alkaline (KOH) and acid (H2SO4) solutions using porous Teflon‐bonded carbon electrodes impregnated with the catalysts. At 700 mV high current densities of 75 mA/cm2 in acid solution and up to 90 mA/cm2 in alkaline solution were obtained.

  DOI：

  10.1002/bbpc.198800335
• 作为试剂：
  描述：

  环己烷 在 [5,10,15,20-tetra(p-nitro)phenylporphyrin]cobalt(II) 、 氧气 作用下， 150.0 ℃ 、1.0 MPa 条件下， 反应 1.0h， 生成 环己酮 、 环己醇
  参考文献：
  名称：

  Catalytic oxidation of cyclohexane by substituted metalloporphyrins: experimental and molecular simulation

  摘要：

  金属卟啉和能量差较低的金属卟啉中间体分别具有更强的活化氧和环己烷的能力。

  DOI：

  10.1039/c5ra14480a

文献信息

• Alkyl Exchange Reactions of Organocobalt Porphyrins. A Bimolecular Homolytic Substitution Reaction
  作者：Alan M. Stolzenberg、Yang Cao

  DOI：10.1021/ja002954v

  日期：2001.9.1

  reversible exchange of the organic axial ligand. The exchange reaction was facile in such solvents as benzene, toluene, dichloromethane, chloroform, and pyridine; was unaffected by total exclusion of light; was faster than would be expected for a homolytic process given known Co-C bond dissociation energies; and was of broad scope with respect to the organic ligand. Methyl, benzyl, primary alkyl, secondary alkyl

  有机钴 (III) 卟啉与可区分的卟啉或四吡咯的钴 (II) 络合物的反应导致有机轴向配体的可逆交换。在苯、甲苯、二氯甲烷、氯仿、吡啶等溶剂中交换反应容易；不受完全排除光的影响；给定已知的 Co-C 键解离能，比均裂过程预期的要快；并且在有机配体方面具有广泛的范围。甲基、苄基、伯烷基、仲烷基和酰基交换，但苯基没有交换。交换均衡的位置与方法的方向无关，并且是非统计的。平衡松弛似乎与二阶过程一致。反应速率随 R 基团的特性而变化，顺序为 Bzl > 或 = Me > Et，大约 n-Pr > i-Pr > i-Bu > 乙酰基，大约新戊基，大约 2-金刚烷基。然而，反应速率的总变化非常小。通过用 TEMPO 或 CO 捕获或通过烷基与过量的不同烷基的卤代烷进行烷基交换来寻找自由基中间体的证据的尝试在与交换反应的多个半衰期相当的时间尺度上没有成功。此外，在5-己烯基的交换反应中未检测到重排产物。
• Cobaltoporphyrin-Catalyzed CO₂/Epoxide Copolymerization: Selectivity Control by Molecular Design
  作者：Carly E. Anderson、Sergei I. Vagin、Wei Xia、Hanpeng Jin、Bernhard Rieger

  DOI：10.1021/ma301205g

  日期：2012.9.11

  salt, shows moderate activity toward cyclization, the 4b–e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b–e in terms of reaction temperature and CO2 pressure is presented

  一系列通式为5,10,15,20-四（对烷氧基）苯基卟啉的氯化钴（III）氯化卟啉（4b - e）和相关的5,10,15,20-tetra（p介绍了-硝基）苯基卟啉氯化钴（4f），并探讨了它们对环氧丙烷（PO）/ CO 2偶联/共聚的反应性。硝基取代的配合物（4f）与鎓盐一起显示出适度的环化活性，而4b - e /鎓体系与四苯基卟啉Co（III）氯化物相比具有更好的共聚活性（4a））高选择性并转化为聚碳酸亚丙酯（PPC）。给出了反应温度和CO 2压力下烷氧基取代的卟啉配合物4b - e的综合共聚行为研究。带有较长烷氧基取代基的配合物表现出最高的聚合活性和分子量，但是，相对于PPC的形成，所有取代的催化剂体系对高温的耐受性均降低。对所得聚合物微结构的研究表明，在较低的聚合温度下，优异的头尾环氧树脂结合性和近乎完美的交替碳酸（碳酸酯）特性。
• 一种经环化和金属化同步反应合成四芳基钴卟啉的方法
  申请人：沅江华龙催化科技有限公司

  公开号：CN111592550A

  公开（公告）日：2020-08-28

  本发明公开了一种经环化和金属化同步反应合成四芳基钴卟啉的方法。在芳香醛、吡咯和钴盐在无水三氯化铝催化下，在DMF溶剂和氮气氛中同步发生环化和金属化反应生成四芳基钴卟啉。反应过程为：搅拌下依次加入无水三氯化铝、芳基醛、吡咯和钴盐到DMF中，加热回流反应一定时间后停止反应，降温，在273K附近放置过夜，抽滤得到钴卟啉晶体。该方法直接使用芳香醛、吡咯和钴盐为原料，不需要使用卟吩，不使用强腐蚀性有机酸作溶剂，在无需采用复杂分离手段的条件下，高产率获得高纯度四芳基钴卟啉，易于实现工业化生产。
• Biomimetic Nitration of Phenols Using Metalloporphyrins/H2O2/NO2 −
  作者：Weizhi Sun、Yaojie Liu、Haibo Zhang、Mo Xian、Huizhou Liu

  DOI：10.1007/s10562-015-1610-8

  日期：2015.11

  An efficient metalloporphyrins/H2O2/NO2 (-) nitration of phenols has been developed. The total yield of nitrophenol could reach up to 55.1 %, which is about 4 and sixfold higher than that of horse radish peroxidase catalysis and peroxynitrite nitration, respectively. Furthermore, the nitration system attained an enhanced regioselectivity of 1.0 o/p ratio, and exhibited a good substrate scope of monophenols. This protocol is environmentally friendly compared with HNO3/H2SO4 nitration, and stable, inexpensive and organic solvent tolerant compared with enzyme catalytic nitration and peroxynitrite nitration reaction.[GRAPHICS].
• Trofimenko, A. A.; Pobedinskii, S. N.; Russkikh, I. V., Journal of applied chemistry of the USSR, 1989, vol. 62, p. 1695 - 1698
  作者：Trofimenko, A. A.、Pobedinskii, S. N.、Russkikh, I. V.、Semeikin, A. S.

  DOI：——

  日期：——