cobalt(II) 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin | 119889-99-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: cobalt(II) 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin
• 英文别名: (5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato)Co；5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin；[(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate dianion)Co]；[Co^II(TDFPP)]；Co(II)TF₂PP；[(F₈TPP)Co]
• CAS: 119889-99-5
• 化学式: C₄₄H₂₀CoF₈N₄
• 分子量: 815.65
• InChiKey: MNZCWVPNPHTZGL-AQZHRKEBSA-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：

  cobalt(II) 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin 、 一氧化氮-15N 以 二氯甲烷 为溶剂， 生成 Co(II)(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin)(¹⁵NO)
  参考文献：
  名称：

  Electronic Structure and Ligand Vibrations in FeNO, CoNO, and FeOO Porphyrin Adducts

  摘要：

  The gaseous ligands, CO, NO, and O-2 interact with the Fe ion in heme proteins largely via backbonding of Fe electrons to the pi* orbitals of the XO (X = C, N, O) ligands. In these FeXO adducts, the Fe-X stretching frequency varies inversely with the X-O stretching frequency, since increased backbonding strengthens the Fe-X bond while weakening the X-O bond. Inverse frequency correlations have been observed for all three ligands, despite differing electronic and geometric structures, and despite variable composition of the "FeX" vibrational mode, in which Fe-X stretching and Fe-X-O coordinates are mixed for bent FeXO adducts. We report experimental data for 5-coordinate Co-II(NO) porphyrin adducts (isoelectronic with Fe-II(OO) adducts), and the results of density functional theory (DFT) modeling for 5-coordinate Fe-II(NO), Co-II(NO), and Fe-II(OO) adducts. Inverse nu(MX)/nu(XO) correlations are obtained computationally, using model porphyrins with graded electron-donating and -withdrawing substituents to modulate the backbonding. Computed slopes agree satisfactorily with experiment, provided nonhybrid functionals are used, which avoid overemphasizing high-spin states. The BP86 functional gives correct ground states, a closed-shell singlet for Co-II(NO) and an open-shell singlet for the isoelectronic Fe-II(OO), as corroborated by structural data for Co-II(NO), and the nu(MX)/nu(XO) slope agreement with experiment for both adducts. However, for Fe-II(OO) adducts, the computed inverse nu(MX)/nu(XO) correlation applies only to porphyrins with electron-donating and withdrawing substituents of moderate strength. For substituents more donating than -CH3, a direct correlation is obtained, the Fe-O and O-O bonds weakening in concert. This effect is ascribed to the dominance of sigma bonding via the in-plane d(xz)(+d(z)(2))-pi* orbital, when electron-donating substituents raise the d orbital energies sufficiently to render backbonding (d(yz)-pi*) unimportant.

  DOI：

  10.1021/ic400364x
• 作为产物：
  描述：

  5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.01h， 生成 cobalt(II) 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin
  参考文献：
  名称：

  Metal Exchange Reactions of o,o′-Dihalosubstituted Cd(II) Tetraphenylporphyrinates with d-Metal Salts in DMF

  摘要：

  DOI：

  10.1134/s1070363221080144

文献信息

• Nitric Oxide Dioxygenase Activity of a Nitrosyl Complex of Cobalt(II) Porphyrinate in the Presence of Hydrogen Peroxide via Putative Peroxynitrite Intermediate
  作者：Baishakhi Mondal、Soumen Saha、Dibyajyoti Borah、Rakesh Mazumdar、Biplab Mondal

  DOI：10.1021/acs.inorgchem.8b02722

  日期：2019.1.22

  1 F8TPP = 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate dianion} in dichloromethane with nitric oxide (NO) led to the nitrosyl complex, [(F8TPP)Co(NO)], 2. Spectroscopic studies and structural characterization revealed it as a bent nitrosyl of CoNO}8 description. It was stable in the presence of dioxygen. However, it reacts with H2O2 in acetonitrile (or THF) solution at −40 °C (or −80 °C)

  钴卟啉配合物[[F 8 TPP）Co]，1 F 8 TPP = 5,10,15,20-四（2,6-二氟苯基）卟啉二价阴离子}与一氧化氮（NO）的反应导致亚硝酰基络合物[[F 8 TPP）Co（NO）]，2。光谱研究和结构表征表明它是CoNO} 8描述的弯曲亚硝酰基。在双氧存在下稳定。但是，它在-40°C（或-80°C）下与乙腈（或THF）溶液中的H 2 O 2反应，生成相应的硝酸钴（III）配合物[[F 8 TPP] Co（NO 3）]，3。该反应大概是通过形成过亚硝酸钴中间体而进行的。X波段电子顺磁共振和电喷雾电离质谱研究表明，[（卟啉）Co（III）-O • ]自由基的中间形成，这反过来又支持了相应的Co（IV）-氧代物质的生成。反应。这与一氧化氮双加氧酶活性中提出的血红素-过亚硝酸盐中O-O键的均质裂解是一致的。此外，还观察到特征性的过氧亚硝酸盐诱导的苯酚环反应。