bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)iron(II) | 17845-65-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)iron(II)
• 英文别名: [(5,10,15,20-tetraphenylporphinate)Fe(piperidine)2]；iron(II) tetraphenylporphyrine di-piperidine；Fe(tetraphenylporphyrin)(piperidine₎₂；FeTPPPip2；Fe(meso-tetraphenylporphyrinato dianion)(piperidine)2；Fe((meso-tetraphenylporphyrin)(-2H))(piperidine)2
• CAS: 17845-65-7
• 化学式: C₅₄H₅₀FeN₆
• 分子量: 838.878
• InChiKey: YLKOAYLQYSTWRN-NBICUONBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)iron(II) 以 solid 为溶剂， 生成 5,10,15,20-TETRAPHENYL-21H,23H-PORPHINE IRON(III) CHLORIDE
  参考文献：
  名称：

  升华固体中氮碱与铁-卟啉亚硝基络合物Fe（Por）（ONO）的相互作用。

  摘要：

  氮路易斯碱（B）1-甲基咪唑（1-MeIm），吡啶（Py）和NH3作为气体与升华层中含有5配位亚硝基铁（III）-卟啉配合物Fe（Por）（eta1）的反应-ONO）（1）被描述（Por =中-四苯基-卟啉基或中-四-对甲苯基-卟啉基二价阴离子）。原位FTIR和光谱用于表征由1与B = 1-MeIm，Py或NH3反应形成的6-配位硝基络合物的形成。这些代表了具有空间上未保护的铁卟啉的6-配位的氨基-硝基配合物的第一个实例。氨在140 K下与Fe（Por）（ONO）的相互作用最初导致亚硝基物种Fe（Por）（NH3）（eta1-ONO），并且该物种异构化为硝基络合物Fe（Por）（NH3）（ η1-NO2）加热至180K。当后者在强力泵送下加热到室温时，初始的亚硝基络合物Fe（Por）（eta1-ONO）被还原。给出了6-配位的铁-卟啉配合物中配位的硝基振动频率的分配，并使用15N标记的二氧

  DOI：

  10.1021/ic700846x
• 作为产物：
  描述：

  哌啶 、 meso-tetraphenylporphyrin iron(III) chloride 以 二氯甲烷 为溶剂， 以48%的产率得到bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)iron(II)
  参考文献：
  名称：

  aμ-Oxo 铬-铁配合物的分子结构：晶体学表征的 μ-Oxo 杂金属卟啉的罕见例子

  摘要：

  μ-氧杂金属卟啉[(pip)(tpp)CrIIIOFeIII(tpp)]（pip =哌啶）的晶体结构不仅证实了铬和铁原子的氧化态，而且揭示了铬周围独特的配位环境（ III)，它基本上从卟啉平面突出。

  DOI：

  10.1246/bcsj.72.1781

文献信息

• Six-Coordinate Nitro Complexes of Iron(III) Porphyrins with <i>trans</i> S-Donor Ligands. Oxo-Transfer Reactivity in the Solid State
  作者：Tigran S. Kurtikyan、Astghik A. Hovhannisyan、Alexei V. Iretskii、Peter C. Ford

  DOI：10.1021/ic901722g

  日期：2009.12.7

  Spectroscopic studies demonstrate that the 5-coordinate O-nitrito complexes Fe(Por)(η1-ONO) (Por - meso-tetraphenyl- or meso-tetra-p-tolyl-porphyrinato dianions) react with the thioethers (R2S) dimethylsulfide and tetrahydrothiophene to give the 6-coordinate N-nitrito complexes Fe(Por)(R2S)(NO2). These reactions were conducted in low-temperature porous layered solids formed in a cryostat; however,

  光谱研究表明，5-坐标O形nitrito络合物的Fe（POR）（η 1 -ONO）（POR -内消旋四苯基或内消旋-四-对-甲苯基-卟啉二价阴离子）与硫醚（R反应2 S）二甲基硫醚和四氢噻吩，得到6配位的N-亚硝酸盐配合物Fe（Por）（R 2 S）（NO 2）。这些反应是在低温恒温器中形成的低温多孔层状固体中进行的。但是，在大气中存在过量的R 2 S时，相同的物质在室温下是中等稳定的。即使对Fe（P）（DMS）（η）进行了DFT计算，也没有在R 2 S近端配体上观察到六坐标的O-硝化异构体。1- ONO）模型和Fe（P）（DMS）（NO 2）模型（P =卟啉二价阴离子，DMS =二甲基硫醚）显示后者仅比前者适度降低能量（〜8 kJ / mol）。在过量R 2 S的存在下，将该系统置于室温下最终导致在FTIR光谱中出现亚硝酰基亚铁Fe（Por）（NO）的ν（NO）谱带特征。气相的质谱图同时显示了亚砜R
• The formation of heterobinuclear µ-oxo Cr–O–Fe porphyrin complexes by the reaction of oxochromium(<scp>IV</scp>) and iron(<scp>II</scp>) porphyrins
  作者：David J. Liston、Keith S. Murray、Bruce O. West

  DOI：10.1039/c39820001109

  日期：——

  δ-tetraphenylporphinato-oxochromium(IV)[(TPP)CrO] with α,β,γ,δ-tetraphenylporphinato-iron(II)bis(piperidine) in toluene results in the formation of the mixed-metal complex (TPP)CrIII–O-FeIII(TPP) characterised by chemical reactions and magnetic measurements [the metal ions are antiferromagneticlly coupled Fe (S= 5/2)-Cr (S= 3/2)]; similar µ-oxo compounds having dissimilar porphyrin ligands on each metal have

  α，β，γ，δ-四苯基卟啉-氧化铬（IV）[（TPP）CrO]与α，β，γ，δ-四苯基卟啉-铁（II）双（哌啶）在甲苯中的反应导致形成混合金属配合物（TPP）Cr III -O-Fe III（TPP），其特征在于化学反应和磁测量[金属离子是反铁磁耦合的Fe（S = 5/2）-Cr（S = 3/2）]；还制备了在每种金属上具有不同卟啉配体的相似的μ-氧代化合物。
• Synthesis and Magnetic Exchange Properties of Linear Trinuclear Oxo-Bridged MIIIORuIVOMIII Complexes (M = Fe, Cr, Mn) Formed by Two-Electron Redox Reactions
  作者：Kevin J. Berry、Boujemaa Moubaraki、Keith S. Murray、Peter J. Nichols、Lewis D. Schulz、Bruce O. West

  DOI：10.1021/ic00120a017

  日期：1995.8

  The two-electron reductions of various porphyrin complexes Ru-VI(O)(2)(P) by Fe(II), Cr(II), and Mn(II) compounds of porphyrins and salicylaldimines result in the formation of heterotrimetallic ore-bridged complexes (L)M(III)-ORuIV(P)OM(III)(L) (M = Fe(III), Cr(III), Mn(III); P is the dianion of 5,10,15,20-tetraarylporphyrins, such as tetraphenylporphyrin (TPP), tetrakis(p-methoxyphenyl)porphyrin (TMP), or 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP); L is TPP, TMP, or OEP or the dianions of N,N'-(4-methyl-4-azaheptane-1,7-diyl)bis(salicylaldimine) (salmah) or N,N'-ethane-1,2-diylbis(salicylaldimine) (salen). A detailed study of the temperature- and field-dependent magnetic properties of this rather novel series of (L)M(III)ORu(IV)(P)OM(III)(L) compounds has been made. The spin-states of the constituent metal centers are as follows: Ru-IV, S-Ru = 1 (d(4)); Fe-III S-Fe = 5/2 (d(5)); Cr-III, S-Cr = 3/2 (d(3)); Mn-III, S-Mn = 4/2 (d(4)). The spin-state and coordination geometry of the (L)Fe-III groups were confirmed by Mossbauer spectral measurements. Trinuclear combinations of the present kind give rise to unusual coupled spin-state energy levels which, in the case of (L)(FeORuIV)-O-III(P)OFeIII(L) compounds, result in ''ferromagnetic-like'' plots of magnetic moment versus temperature, particularly at low temperatures. The following best-fit values of parameters were deduced from the magnetic moment data, obtained in 1 T fields over the temperature range 4.2-300 K. (salmah)FeORu(TPP)OFe(salmah): g = 1.97, J(12) = -19.7 cm(-1), J(13) = +6.5 cm(-1), alpha J(13)/J(12) = -0.33, ground-state S = 4; (TMP)FeORu(TPP)OFe(TMP): g = 1.95, J(12) = -23.4 cm(-1), J(13) = 5.4 cm(-1), alpha = -0.23, ground-state S = 4. (TPP)FeORu(TPP)OFe(TPP): g = 2.0, J(12) = -35.7 cm(-1), J(13) = 11.2 cm(-1), alpha = -0.31, ground-state S = 4, [(TPP)Fe]O-2 impurity = 13%, zero-field splitting of the S = 4 state (D cm approximate to 5 cm(-1)). (TMP)MnORu(TPP)OMn(TMP): g = 1.93, J(12) = -17.4 cm(-1), J(13) = 9.6 cm(-1), alpha = -0.55, groundstate S = 3. (TPP)CrORu(TPP)OCr(TPP): g = 1.98, J(12) = -25.3 cm(-1), J(13) = -11.1 cm(-1), alpha = 0.44, groundstate S = 1. Possible reasons for the small sizes of the J(12) values, in comparison to those of related M(III)OM(III) and (RuORuIV)-O-IV compounds, are discussed.
• Reactions of Nitrogen Oxides with Heme Models: Spectral Characterization of an Elusive Five-Coordinate FeIII(porphyrin) Nitrito Intermediate
  作者：Tigran S. Kurtikyan、Peter C. Ford

  DOI：10.1002/anie.200502409

  日期：2006.1.9
• Nanthakumar, Alaganandan; Nasir, M. Sarwar; Karlin, Kenneth D., Journal of the American Chemical Society, 1992, vol. 114, p. 6564 - 6566
  作者：Nanthakumar, Alaganandan、Nasir, M. Sarwar、Karlin, Kenneth D.、Ravi, Natarajan、Huynh, Boi Hanh

  DOI：——

  日期：——