(tetrakis(2,6-difluorophenyl)porphyrin)iron(II)-(piperidine)2 | 141981-26-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (tetrakis(2,6-difluorophenyl)porphyrin)iron(II)-(piperidine)2
• CAS: 141981-26-2
• 化学式: C₅₄H₄₂F₈FeN₆
• 分子量: 982.802
• InChiKey: VSLXSTYKGFCZNI-CXJMORQYSA-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：

  (tetrakis(2,6-difluorophenyl)porphyrin)iron(II)-(piperidine)2 、 {(tris(2-pyridylmethyl)amine)(acetonitrile)copper(I)} perchlorate 在 O₂ 作用下， 以 二氯甲烷 为溶剂， 以40%的产率得到{((tris(2-pyridylmethyl)amine)(acetonitrile)copper(II))(μ-O)(tetrakis(2,6-difluorophenyl)porphyrinate(2-)iron(III))} perchlorate
  参考文献：
  名称：

  X-ray Structure and Physical Properties of the Oxo-Bridged Complex [(F8-TPP)Fe-O-Cu(TMPA)]+, F8-TPP = Tetrakis(2,6-difluorophenyl)porphyrinate(2-), TMPA = Tris(2-pyridylmethyl)amine: Modeling the Cytochrome c Oxidase Fe-Cu Heterodinuclear Active Site

  摘要：

  The iron/copper heterodinuclear center in cytochrome c oxidases has attracted the interest of inorganic chemists since this is the site of dioxygen (O-2) four-electron four-proton reduction to water by the reduced enzyme, while the oxidized (''resting'') isolated protein dinuclear center exhibits unusual physical, spectroscopic, and ligand-binding properties. We describe here a model compound, [(F-8-TPP)Fe-III-O-Cu-II(TMPA)](+) (3), generated directly from O-2-reduction by 1:1 mixtures of the reduced copper(I) and iron(II) complexes [(TMPA)Cu-I(CH3CN)](+) (1) (TMPA = tris(2-pyridylmethyl)amine) and (F-8-TPP)Fe-II(pip)(2) (2) (F-8-TPP = tetrakis(2,6-difluorophenyl)porpyrinate-(2-), pip = piperidine) in O-2-saturated CH2Cl2 at -80 degrees C; warming to 0 degrees C, followed by precipitation with diethyl ether, affords 3 in similar to 70% yield, An X-ray diffraction study on [(F-8-TPP)Fe-O-Cu(TMPA)](ClO4).3C(7)H(8).2CH(3)CN (3-ClO4) as well as the mu-oxo iron dimer [(F-8-TPP)Fe]O-2.3C(7)H(8) allows for direct structural cc,mparisons, as well as with other relevant compounds. Compound 3 also possesses a linear mu-oxo-bridging ligand, where angle Fe-O-Cu = 178.2-(4)degrees; unusually short metal-oxygen distances of Fe-O = 1.740(5) Angstrom and Cu-O = 1.856(5) Angstrom are observed, and Fe...Cu = 3.596(2) Angstrom. The coordination geometry around Cu is distorted from the usual (i.e., for TMPA-Cu(II) complexes) trigonal-bipyramidal configuration toward a square-based pyramidal arrangement, and the three pyridine rings are situated between the four F-8-TPP phenyl rings, thus leaving one ''slot'' free. H-1-NMR spectra of 3-ClO4 in CD2Cl2 exhibit a pyrrole signal at 65 ppm (corroborated by H-2-NMR) which is upfield shifted relative to ol her axially symmetric high-spin (tetraphenylporphyrinate)iron(III) complexes; this is consistent with electronic/maegnetic coupling of the Fe(III) and Cu(II) centers. Additional upfield-shifted signals are tentatively assigned to the TMPA ligand on copper, thus implicating a bridged structural arrangement which is maintained in solution. A detailed magnetic Mossbauer spectroscopic study (4.2 K at 0, 0.5, and 8 T) has been carried out.The data unambiguously indicate that 3 possesses a high-spin ferric (S-Fe = 5/2) ion and exhibits characteristic parameters: D = 6.0 +/- 0.5 cm(-1) E/D = 0.03 +/- 0.01, Delta E(Q) = -1.26 +/- 0.02 mm/s, eta = 0, delta = 0.46 +/- 0.01 mm/s, and A/g(n) beta(n) = -23.7 +/- 0.3 T. Furthermore, the magnetic properties observed, i.e., in the presence or absence of an applied field, demonstrate that the ferric ion is spin-coupled to the cupric ion to form an overall integer spin system in [(F-8-TPP)(FeO)-O-III-Cu-II(TMPA)](ClO4) (3-ClO4). The Mossbauer isomer shift and quadrupole splitting parameters compare favorably with those previously obtained for data on enzyme resting-state preparations, although they differ in certain details. The conclusion that 3-ClO4 is an S = 2 system is determined by multifield saturation magnetization measurements, carried out both in solution (2-200 K) and the solid state (30-300 K). An exact magnetic coupling constant J (for exchange coupling according to (-2JS(1).S-2)) could not be determined from the solution data, due to the inherent ''noise'' found in these measurements, even for similar to 1 mM solutions. These findings carl into question previous evaluations for the lower limit of \J\ greater than or equal to 200 cm(-1) for the dinuclear Fe(III)-X-Cu(II) site in as-isolated ''resting'' oxidized cytochrome c oxidase enzyme; a lower limit of \J\ greater than 50 cm(-1) is suggested as a better estimate. Solid-state measurements on 3-ClO4 give a value of -J = 87 cm(-1), i.e., moderately strong antiferromagnetic coupling between high-spin iron(III) and copper(II) ions, consistent with the NMR and Mossbauer spectroscopic data. The possible biological relevance of the oxo-bridged complex [(F-8-TPP)Fe-III-O-Cu-II(TMPA)]ClO4) (3-ClO4) and its observed magnetic/electronic properties are discussed.

  DOI：

  10.1021/ja00090a023
• 作为产物：
  描述：

  哌啶 、 5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride 以 二氯甲烷 为溶剂， 以60%的产率得到(tetrakis(2,6-difluorophenyl)porphyrin)iron(II)-(piperidine)2
  参考文献：
  名称：

  X-ray Structure and Physical Properties of the Oxo-Bridged Complex [(F8-TPP)Fe-O-Cu(TMPA)]+, F8-TPP = Tetrakis(2,6-difluorophenyl)porphyrinate(2-), TMPA = Tris(2-pyridylmethyl)amine: Modeling the Cytochrome c Oxidase Fe-Cu Heterodinuclear Active Site

  摘要：

  The iron/copper heterodinuclear center in cytochrome c oxidases has attracted the interest of inorganic chemists since this is the site of dioxygen (O-2) four-electron four-proton reduction to water by the reduced enzyme, while the oxidized (''resting'') isolated protein dinuclear center exhibits unusual physical, spectroscopic, and ligand-binding properties. We describe here a model compound, [(F-8-TPP)Fe-III-O-Cu-II(TMPA)](+) (3), generated directly from O-2-reduction by 1:1 mixtures of the reduced copper(I) and iron(II) complexes [(TMPA)Cu-I(CH3CN)](+) (1) (TMPA = tris(2-pyridylmethyl)amine) and (F-8-TPP)Fe-II(pip)(2) (2) (F-8-TPP = tetrakis(2,6-difluorophenyl)porpyrinate-(2-), pip = piperidine) in O-2-saturated CH2Cl2 at -80 degrees C; warming to 0 degrees C, followed by precipitation with diethyl ether, affords 3 in similar to 70% yield, An X-ray diffraction study on [(F-8-TPP)Fe-O-Cu(TMPA)](ClO4).3C(7)H(8).2CH(3)CN (3-ClO4) as well as the mu-oxo iron dimer [(F-8-TPP)Fe]O-2.3C(7)H(8) allows for direct structural cc,mparisons, as well as with other relevant compounds. Compound 3 also possesses a linear mu-oxo-bridging ligand, where angle Fe-O-Cu = 178.2-(4)degrees; unusually short metal-oxygen distances of Fe-O = 1.740(5) Angstrom and Cu-O = 1.856(5) Angstrom are observed, and Fe...Cu = 3.596(2) Angstrom. The coordination geometry around Cu is distorted from the usual (i.e., for TMPA-Cu(II) complexes) trigonal-bipyramidal configuration toward a square-based pyramidal arrangement, and the three pyridine rings are situated between the four F-8-TPP phenyl rings, thus leaving one ''slot'' free. H-1-NMR spectra of 3-ClO4 in CD2Cl2 exhibit a pyrrole signal at 65 ppm (corroborated by H-2-NMR) which is upfield shifted relative to ol her axially symmetric high-spin (tetraphenylporphyrinate)iron(III) complexes; this is consistent with electronic/maegnetic coupling of the Fe(III) and Cu(II) centers. Additional upfield-shifted signals are tentatively assigned to the TMPA ligand on copper, thus implicating a bridged structural arrangement which is maintained in solution. A detailed magnetic Mossbauer spectroscopic study (4.2 K at 0, 0.5, and 8 T) has been carried out.The data unambiguously indicate that 3 possesses a high-spin ferric (S-Fe = 5/2) ion and exhibits characteristic parameters: D = 6.0 +/- 0.5 cm(-1) E/D = 0.03 +/- 0.01, Delta E(Q) = -1.26 +/- 0.02 mm/s, eta = 0, delta = 0.46 +/- 0.01 mm/s, and A/g(n) beta(n) = -23.7 +/- 0.3 T. Furthermore, the magnetic properties observed, i.e., in the presence or absence of an applied field, demonstrate that the ferric ion is spin-coupled to the cupric ion to form an overall integer spin system in [(F-8-TPP)(FeO)-O-III-Cu-II(TMPA)](ClO4) (3-ClO4). The Mossbauer isomer shift and quadrupole splitting parameters compare favorably with those previously obtained for data on enzyme resting-state preparations, although they differ in certain details. The conclusion that 3-ClO4 is an S = 2 system is determined by multifield saturation magnetization measurements, carried out both in solution (2-200 K) and the solid state (30-300 K). An exact magnetic coupling constant J (for exchange coupling according to (-2JS(1).S-2)) could not be determined from the solution data, due to the inherent ''noise'' found in these measurements, even for similar to 1 mM solutions. These findings carl into question previous evaluations for the lower limit of \J\ greater than or equal to 200 cm(-1) for the dinuclear Fe(III)-X-Cu(II) site in as-isolated ''resting'' oxidized cytochrome c oxidase enzyme; a lower limit of \J\ greater than 50 cm(-1) is suggested as a better estimate. Solid-state measurements on 3-ClO4 give a value of -J = 87 cm(-1), i.e., moderately strong antiferromagnetic coupling between high-spin iron(III) and copper(II) ions, consistent with the NMR and Mossbauer spectroscopic data. The possible biological relevance of the oxo-bridged complex [(F-8-TPP)Fe-III-O-Cu-II(TMPA)]ClO4) (3-ClO4) and its observed magnetic/electronic properties are discussed.

  DOI：

  10.1021/ja00090a023

文献信息

• 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：——