iron(II) nitrosyl meso-(tetraphenyl) porphyrinate | 70622-46-7

• 英文名称: iron(II) nitrosyl meso-(tetraphenyl) porphyrinate
• 英文别名: (TPP)Fe(NO)(1+)；[Fe(TPP)NO](+)；[Fe(5,10,15,20-tetrakis-phenyl-porphyrinato)(NO)](1+)；ferrous nitrosyl tetraphenylporphyrin cation；[Fe(TPP)(NO)](1+)
• CAS: 70622-46-7
• 化学式: C₄₄H₂₈FeN₅O
• 分子量: 698.586
• InChiKey: KVQVITCLJBEKMV-YKKPBKTHSA-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：

  meso-tetraphenylporphyrin iron(III) chloride 在 氧化亚氮 作用下， 以 甲醇 为溶剂， 26.84 ℃ 、0.0 Pa 条件下， 生成 iron(II) nitrosyl meso-(tetraphenyl) porphyrinate
  参考文献：
  名称：

  Naked Five-Coordinate Fe^III(NO) Porphyrin Complexes: Vibrational and Reactivity Features

  摘要：

  Model ferric heme nitrosyl complexes, [Fe(TPP)(NO)](+) and [Fe(TPFPP)(NO)](+), where TPP is the dianion of 5,10,15,20-tetrakis-phenyl-porphyrin and TPFPP is the dianion of 5,10,15,20-tetrakis-pentafluorophenyl-porphyrin, have been obtained as isolated species by the gas phase reaction of NO with [Fe-III(TPP)](+) and [Fe-III(TPFPP)](+) ions delivered in the gas phase by electrospray ionization, respectively. The so-formed nitrosyl complexes have been characterized by vibrational spectroscopy also exploiting N-15-isotope substitution in the NO ligand. The characteristic NO stretching frequency is observed at 1825 and 1859 cm(-1) for [Fe-III(TPP)(NO)](+) and [Fe-III(TPFPP)(NO)](+) ions, respectively, providing reference values for genuine five-coordinate Fe-III(NO) porphyrin complexes differing only for the presence of either phenyl or pentafluorophenyl substituents on the meso positions of the porphyrin ligand. The vibrational assignment is aided by hybrid density functional theory (DFT) calculations of geometry and electronic structure and frequency analysis which clearly support a singlet spin electronic state for both [Fe(TPP)(NO)](+) and [Fe(TPFPP)(NO)](+) complexes. Both TD-DFT and CASSCF calculations suggest that the singlet ground state is best described as Fe-II(NO+) and that the open-shell AFC bonding scheme contribute for a high-energy excited state. The kinetics of the NO addition reaction in the gas phase are faster for [Fe-III(TPFPP)](+) ions by a relatively small factor, though highly reliable because of a direct comparative evaluation. The study was aimed at gaining vibrational and reactivity data on five-coordinate Fe-III(NO) porphyrin complexes, typically transient species in solution, ultimately to provide insights into the nature of the Fe(NO) interaction in heme proteins.

  DOI：

  10.1021/ic200073v

文献信息

• Five- and Six-Coordinated Nitrosyl Iron(II) Complexes of Tetrakis (<i>p</i>-substituted phenyl)porphyrins. Substituent Effects on the EPR Parameters and the NO Stretching Frequencies
  作者：Tetsuhiko Yoshimura

  DOI：10.1246/bcsj.64.2819

  日期：1991.9

  Five- and six-coordinated nitrosyl iron(II) complexes of a series of tetrakis(p-substituted phenyl)porphyrins have been prepared. Their EPR and IR spectra have been measured and analyzed in order to elucidate the cis-effect of substituents on the axial nitrosyl ligand. As the first redox potentials of the free base porphyrins in the complexes became positive, the NO stretching frequencies increased

  已经制备了一系列四（对取代苯基）卟啉的五和六配位亚硝酰基铁（II）配合物。已经测量和分析了它们的 EPR 和 IR 光谱，以阐明取代基对轴向亚硝酰基配体的顺式效应。随着复合物中游离碱卟啉的第一个氧化还原电位变正，五配位和六配位亚硝基（卟啉）铁（II）复合物中的 NO 拉伸频率增加，在轴向位点有一个含氮碱基转移到没有组。氧化还原电位的正移导致 EPR g 值和超精细耦合常数在室温和 77 K 下五配位配合物的增加，而它导致 g 值的降低和六配位配合物的超精细耦合常数略有增加。这些结果是合理的，因为随着卟啉外围取代基的吸电子能力增强，铁与 NO 的键...
• Bari, Sara E.; Marti, Marcelo A.; Amorebieta, Valentin T., Journal of the American Chemical Society, 2003, vol. 125, p. 15271 - 15273
  作者：Bari, Sara E.、Marti, Marcelo A.、Amorebieta, Valentin T.、Estrin, Dario A.、Doctorovich, Fabio

  DOI：——

  日期：——
• Mu; Kadish, Inorganic Chemistry, 1990, vol. 29, # 5, p. 1031 - 1036
  作者：Mu、Kadish

  DOI：——

  日期：——