2,3-dibromo-5,10,15,20-tetraphenylporphyrinatonickel(II) | 253134-81-5

• 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: 2,3-dibromo-5,10,15,20-tetraphenylporphyrinatonickel(II)
• 英文别名: nickel(II) 2,3-dibromo-5,10,15,20-tetraphenylporphyrin；[Ni(II)(2,3-dibromo-5,10,15,20-tetraphenylporphirin)]
• CAS: 253134-81-5
• 化学式: C₄₄H₂₆Br₂N₄Ni
• 分子量: 829.215
• InChiKey: BZHOSNLOLLSBRB-KRRVLKABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.02
• 重原子数：
  51.0
• 可旋转键数：
  4.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,3-dibromo-5,10,15,20-tetraphenylporphyrinatonickel(II) 在 甲醇 、 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 生成 nickel(II) 2,3-diethynyl-5,10,15,20-tetraphenylporphyrin
  参考文献：
  名称：

  PtCl2-catalyzed benzannulation of nickel(II) 2,3-dialkynylporphyrins to form unusual phenanthroporphyrins

  摘要：

  Reaction of Ni(II) 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with substituted stannyl alkynes generates substituted 2,3-dialkynylporphyrins in good yields. Thermolysis of these motifs with stoichiometric or even catalytic equivalents of PtCl2 yields unusual phenanthroporphyrins with only small amounts of the established picenoporphyrin or other side products. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.07.008
• 作为产物：
  描述：

  nickel(II) acetate tetrahydrate 、 2,3-dibromo-5,10,15,20-tetraphenylporphyrin 以 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 生成 2,3-dibromo-5,10,15,20-tetraphenylporphyrinatonickel(II)
  参考文献：
  名称：

  区域选择性 2,3-二取代卟啉：合成、光谱、结构和电化学性质

  摘要：

  一系列区域选择性 β-二取代内消旋-四苯基卟啉 H 2 TPP(X) 2（其中 X = 甲基 (CH 3 )、苯基 (Ph)、溴 (Br) 和苯乙炔基 (PE)），以及它们的金属络合物 (合成了Cu( II )、Co( II )、Ni( II ) 和 Zn( II ))，并使用各种光谱技术对其进行了表征。苯乙炔基取代的卟啉 H 2 TPP(PE) 2的吸收带在 Soret 带中表现出相当大的红移 6-18 nm，在 Q x (0,0) 带中表现出 10-25 nm 与甲基-和苯基-二取代的卟啉，即。H 2 TPP(CH 3 ) 2和H 2 TPP(Ph) 2。这种红移归因于卟啉 π 骨架上存在的苯基和苯乙炔基的感应和共振效应，并遵循 H 2 TPP(CH 3 ) 2 < H 2 TPP(Ph) 2 < H 2 TPP( PE) 2。在这些区域选择性 β-二取代游离碱基卟啉中发生两个连续的单

  DOI：

  10.1039/d3nj01288c

文献信息

• Accelerated Bergman cyclization of porphyrinic-enediynesElectronic supplementary information (ESI) available: syntheses, characterization of 2a–4b, crystallographic files (CCDC 200680–200685) in CIF format. See http://www.rsc.org/suppdata/cc/b2/b212923j/
  作者：Mahendra Nath、John C. Huffman、Jeffrey M. Zaleski

  DOI：10.1039/b212923j

  日期：2003.3.24

  The Bergman cyclization of simple diethynylporphyrinic-enediynes exhibits a double activation barrier to the formation of Bergman cyclized product. Addition of H-atom acceptor accelerates the formation of the picenoporphyrin, indicating that the second barrier is rate limiting.

  简单的双乙炔基卟啉母烯二炔通过伯格曼环化反应生成了伯格曼环化的产物，但其具有双重活化能障碍。添加氢原子受体可加速picenoporphyrin的形成，这表明第二个能垒是速率限制因素。
• Unusual Aryl−Porphyrin Rotational Barriers in Peripherally Crowded Porphyrins
  作者：Craig J. Medforth、Raid E. Haddad、Cinzia M. Muzzi、Neal R. Dooley、Laurent Jaquinod、David C. Shyr、Daniel J. Nurco、Marilyn M. Olmstead、Kevin M. Smith、Jian-Guo Ma、John A. Shelnutt

  DOI：10.1021/ic010958a

  日期：2003.4.1

  aryl-porphyrin rotational barrier and the core substituent M in some novel 2,3,5,7,8,10,12,13,15,17,18,20-dodecaarylporphyrins (DArPs), and specifically in some 5,10,15,20-tetraaryl-2,3,7,8,12,13,17,18-octaphenylporphyrins (TArOPPs), where steric crowding of the peripheral groups always results in a very nonplanar macrocycle. X-ray structures of DArPs indicate differences in the nonplanar conformation of the

  先前对5,10,15,20-四芳基卟啉的研究表明，介孔芳基卟啉旋转的势垒（DelTAG ++（ROT））随核心取代基M的变化而变化，而对于小金属（M = Ni）较低与大型金属（M = Zn）相比，对金属离子而言（M = 4H（2+））与游离碱卟啉（M = 2H）比较。这归因于卟啉环的非平面畸变的变化和由核取代基引起的大环的可变形性。在本工作中，使用X射线晶体学，分子力学（MM）计算和可变温度（VT）（1）H NMR光谱法研究了一些新型化合物中芳基卟啉旋转势垒与核心取代基M的关系。 2,3,5,7,8,10,12,13,15,17,18,20-十二烷基芳基卟啉（DArPs），特别是在5,10,15,20-四芳基-2,3,7,8 ，12,13，17,18-八苯基卟啉（TArOPP），其中外围基团的空间拥挤总是导致非常不平坦的大环。DArP的X射线结构表明，大环的非平面构象随M的变化，对于M =
• Multicarbocycle Formation Mediated by Arenoporphyrin 1,4-Diradicals: Synthesis of Picenoporphyrins
  作者：Hidenori Aihara、Laurent Jaquinod、Daniel J. Nurco、Kevin M. Smith

  DOI：10.1002/1521-3773(20010917)40:18<3439::aid-anie3439>3.0.co;2-z

  日期：2001.9.17
• Ambient Temperature Activation of Haloporphyrinic-Enediynes:  Electronic Contributions to Bergman Cycloaromatization
  作者：Mahendra Nath、John C. Huffman、Jeffrey M. Zaleski

  DOI：10.1021/ja0302782

  日期：2003.9.1

  We have synthesized the nickel(II) 2,3-bis(haloethynyl)-5,10,15,20-tetraphenylporphyrins with -Br (2a) or -I (2b) at the alkyne termini position from the corresponding 2,3-diethynyl analogue (1). The cross coupling of nickel(II) 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with trimethyl(trimethylstannanylethynyl)silane in the presence of a Pd0 catalyst and subsequent deprotection with base under aqueous conditions yields the nickel(II) 2,3-diethynyl-5,10,15,20-tetraphenylporphyrin (1). Subsequent reaction of 1 with N-bromo- or N-iodosuccinimide in dry acetone in the presence of AgNO3 yields 2,3-bis(haloethynyl)-5,10,15,20-tetraphenylporphyrins in 70% (2a) and 68% (2b) yields. The X-ray crystal structures of 2a,b show that the porphyrin backbone deviates significantly from planarity due to a Ni(II)-induced mixture of the classic ruffle and saddle distortions. Thermolysis of 2a at 190 degrees C for 6 h in chlorobenzene and 30-fold 1,4-cyclohexadiene (CHD) generates the Bergman cyclized nickel(II) dibromopicenoporphyrin product (3) in 65% yield, which derives from diradical addition across the adjacent meso-phenyl substituents. Similarly, nickel(II) 2,3-bis(iodoethynyl)-5,10,15,20-tetraphenylporphyrin, 2b, cyclizes at 190 degrees C in chlorobenzene/CHD via high-temperature substitution of iodine by hydrogen (from CHD) or chlorine (from solvent) to afford a mixture of 4 (15%) and 5 (45%). Remarkably, ambient temperature incubation of 2a in MeOH/CHCl3 (1:3, 22 h) or chlorobenzene/CHD (3:1, 24 h) leads to generation of 3 in 15% and 22% isolated yields, respectively. Addition of 1.2 equiv of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in CHCl3/MeOH dramatically accelerates the rate of reaction, producing 3 in 30% yield within 0.5 h. The origin of the ambient temperature activation of 2a derives from the ability of electron-withdrawing functionalities at the alkyne termini to decrease the activation barrier to the Bergman product.