[Ni(II)(picenoporphyrin)] | 380447-58-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: [Ni(II)(picenoporphyrin)]
• 英文别名: nickel(II)10,15-diphenyl-piceno[20,1,2,3,4,5-fghij]porphyrin
• CAS: 380447-58-5
• 化学式: C₄₈H₂₆N₄Ni
• 分子量: 717.451
• InChiKey: HLOPHNFGNMQMPG-MPBMNXIUSA-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

• 作为产物：
  描述：

  nickel(II) 2,3-diethynyl-5,10,15,20-tetraphenylporphyrin 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 0.5h， 生成 [Ni(II)(picenoporphyrin)]
  参考文献：
  名称：

  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/

  摘要：

  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。

  DOI：

  10.1039/b212923j

文献信息

• PtCl2-catalyzed benzannulation of nickel(II) 2,3-dialkynylporphyrins to form unusual phenanthroporphyrins
  作者：Mahendra Nath、Maren Pink、Jeffrey M. Zaleski

  DOI：10.1016/j.jorganchem.2011.07.008

  日期：2011.12

  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.
• 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.