meso-tetraphenylporphyrinato(η1-nitrito)(nitrosyl)iron | 880172-71-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: meso-tetraphenylporphyrinato(η1-nitrito)(nitrosyl)iron
• 英文别名: trans-Fe(TPP)(NO2)(NO)；trans-Fe(5,10,15,20-tetraphenyl-21H, 23H-porphine)(NO2)(NO)；Fe(meso-tetraphenylporphyrinato(2-))(η1-ONO)(NO)；[(5,10,15,20-tetraphenylporphyrinato)Fe(NO)(NO2)]；Fe(tetraphenylphorphirinato)(nitrosyl)(nitrito)；[(meso-tetraphenylporphyrinate)Fe(ONO)(NO)]
• CAS: 880172-71-4；89935-21-7；935699-71-1
• 化学式: C₄₄H₂₈FeN₆O₃
• 分子量: 744.592
• InChiKey: XSAPPEWUSNJXJE-NBICUONBSA-M

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：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  [Fe(tetraphenylporphinate)(NO2)(NO)] 以 potassium bromide 为溶剂， 生成 meso-tetraphenylporphyrinato(η1-nitrito)(nitrosyl)iron
  参考文献：
  名称：

  Single- and Double-Linkage Isomerism in a Six-Coordinate Iron Porphyrin Containing Nitrosyl and Nitro Ligands

  摘要：

  Density Functional theoretical calculations confirm the experimental observation that the low-temperature photolysis of (TPP)Fe(NO)(NO2) (as a KBr pellet) results in the generation of linkage isomers involving the axial NO and NO2 groups and suggest the possible formation of the double linkage isomer (TPP)Fe(ON)(ONO). The energy difference between the ground state (porphine)Fe(NO)(NO2) and the double-linkage isomer (porphine)Fe(ON)(ONO) is 1.57 eV, which is comparable to the 1.59 eV calculated previously for the nitrosyl-to-isonitrosyl linkage isomerism in the five-coordinate (porphine)Fe(NO) analogue.

  DOI：

  10.1021/ja0488986

文献信息

• Electronic Structure of Six-Coordinate Iron(III)−Porphyrin NO Adducts: The Elusive Iron(III)−NO(radical) State and Its Influence on the Properties of These Complexes
  作者：V. K. K. Praneeth、Florian Paulat、Timothy C. Berto、Serena DeBeer George、Christian Näther、Corinne D. Sulok、Nicolai Lehnert

  DOI：10.1021/ja801860u

  日期：2008.11.19

  further reveal that the thermodynamic weakness of the Fe-NO bond in ferric heme nitrosyls is an intrinsic feature that relates to the properties of the high-spin Fe(III)-NO(radical) (S = 2) state that appears at low energy and is dissociative with respect to the Fe-NO bond. Altogether, release of NO from a six-coordinate ferric heme nitrosyl requires the system to pass through at least three different

  本文研究了五配位铁血红素与结合的轴向咪唑配体和一氧化氮 (NO) 之间的相互作用。相应的模型复合物 [Fe(TPP)(MI)(NO)](BF4)（MI = 1-甲基咪唑）使用振动光谱法与正态坐标分析和密度泛函理论 (DFT) 计算相结合进行研究。特别是，核共振振动光谱用于识别 Fe-N(O) 伸缩振动。结果揭示了该复合物通常的 Fe(II)-NO(+) 基态，其特征是强 Fe-NO 和 NO 键，Fe-NO 和 NO 力常数分别为 3.92 和 15.18 mdyn/A。这与 Fe(II) 和 NO(+) 之间的两个强 pi 反键有关。然后研究了另一种基态低自旋 Fe(III)-NO(自由基) (S = 0)。DFT 计算表明，这种状态作为稳定的最小值存在，能量惊人地低，仅比 Fe(II)-NO(+) 基态高约 1-3 kcal/mol。此外，Fe(II)-NO(+) 势能面 (PES) 以非常小的
• Comparative IR Study of Nitric Oxide Reactions with Sublimed Layers of Iron(II)− and Ruthenium(II)−<i>meso</i>-Tetraphenylporphyrinates
  作者：Tigran S. Kurtikyan、Garik G. Martirosyan、Ivan M. Lorkovic'、Peter C. Ford

  DOI：10.1021/ja0269688

  日期：2002.8.1

  layers of Fe(II)(TPP) and Ru(II)(TPP), obtained by sublimation onto low-temperature substrate (77 K), has been investigated by means of IR spectroscopy (TPP = meso-tetraphenylporphyrinate). Only simple addition of NO to form Fe(TPP)(NO) is observed for the iron-porphyrin Fe(II)(TPP), while, in contrast, Ru(II)(TPP) promotes NO disproportionation to form the nitrosyl-nitrito complex Ru(TPP)(NO)(ONO)

  一氧化氮气体与 Fe(II)(TPP) 和 Ru(II)(TPP) 薄层的相互作用已通过红外光谱 (TPP =内消旋四苯基卟啉酸盐）。对于铁卟啉 Fe(II)(TPP) 仅观察到简单的 NO 添加形成 Fe(TPP)(NO)，而相反，Ru(II)(TPP) 促进 NO 歧化形成亚硝酰基-亚硝基络合物 Ru(TPP)(NO)(ONO) 和 N(2)O。Fe(TPP)(NO) 的薄层对于与过量的 NO 进一步反应是惰性的；然而，当将微量分子氧添加到 NO 气氛中时，很容易形成亚硝酰-硝基复合物 Fe(TPP)(NO)(NO(2))。当 NO/NO(2) 混合物中的 NO(2) 浓度相对较高时，也会形成硝基复合物 Fe(TPP)(NO(3))。给出的光谱数据表明，Fe(TPP)(NO) 的亚硝酰基拉伸频率的适度变化是由于晶体堆积效应，而不是由于早期出版物中提出的配位 NO 与质子污染物的 H 键合。通过从含有
• O Atom Transfer from Nitric Oxide Catalyzed by Fe(TPP)
  作者：Rong Lin、Patrick J. Farmer

  DOI：10.1021/ja993643r

  日期：2001.2.1

  The reaction of NO-Fe(TPP) with low pressures of NO gas proceeds through three distinct transformations, the first of which we suggest is the formation of an N-N-coupled, (NO)(2) adduct intermediate. The subsequent formation of NO(NO2)Fe(TPP), which under these conditions readily loses NO, suggests that it is formed by addition of free NO2 to the starting nitrosyl, A mechanism is proposed which implies that the addition of a competitive O atom acceptor would lead to catalytic production of N2O. In agreement with the proposed mechanism, the formation of N2O is decoupled from the formation of the nitrite by using PPh3 as the competitive acceptor. The mechanism of O atom transfer was examined by cross-labeling experiments, which show that both O atoms in the intermediate are equivalent, even under catalytic conditions. The formation of an intermediate was confirmed by IR spectroscopy of the heterogeneous reaction of an NO:Fe(TPP) film with gaseous NO, in which transient, isotope-sensitive nu (NO) bands are seen prior to NO(NO2)Fe(TPP) formation. Mixed N-14/N-15 label experiments demonstrate coupling between the two bound nitrosyls in the transient species.