(2,3,7,8,12,13,17,18-octaethylporphinato)perchloratomanganese(III) | 166821-28-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (2,3,7,8,12,13,17,18-octaethylporphinato)perchloratomanganese(III)
• CAS: 166821-28-9；219736-76-2
• 化学式: C₃₆H₄₄ClMnN₄O₄
• 分子量: 687.161
• InChiKey: SYWZXQTXFBQOTC-YAJYDHHFSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  46.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  146.22
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2,3,7,8,12,13,17,18-octaethylporphinato)perchloratomanganese(III) 、 水 以 二氯甲烷 为溶剂， 生成 (μ-hydroxo)bis(octaethylporphyrinato)manganese(III) perchlorate * 3 CH2Cl2
  参考文献：
  名称：

  A Novel Dimanganese(III) Complex with a Single Hydroxo Bridge. Syntheses, Structures, and Magnetic Susceptibilities of (.mu.-Hydroxo)bis((octaethylporphinato)manganese(III)) Perchlorate and a Monomeric Precursor, Aquo(octaethylporphinato)manganese(III) Perchlorate

  摘要：

  The synthesis and structural and magnetic characterization of a dimanganese(III) complex with a novel, single, hydroxo bridge is described. The complex, (mu-hydroxo)bis((octaethylporphinato)manganese(III)) perchlorate, can be prepared by protonation of an ore-bridged manganese complex or, more reliably, by hydrolysis of monomeric manganese(III) octaethylporphyrinates. The crystal and molecular structure has been solved using X-ray diffraction data collected with an area detector. The two five-coordinate manganese(III) ions in {[Mn(OEP)](2)(OH)}ClO4 are bridged by a single hydroxo ligand with an average Mn-O distance of 2.011 Angstrom and a Mn-O(H)-Mn bridge angle of 152.73 degrees. The average Mn-N-p distance is 2.006 Angstrom. The two porphyrin rings are crowded against each other and are hence canted with a dihedral angle of 12.7 degrees. An additional distortion from ring crowding occurs in the coordination angles O-Mn-N-p at one manganese(III) ion but not at the other. The magnetic susceptibility of the hydroxo-bridged complex has been measured over the temperature range 2-300 K. The observed behavior is typical of an exchange-coupled binuclear complex. The data have been fit to the total spin Hamiltonian (H-tot = H(1) + H(2) - 2J (S) over right arrow(1) .(S) over right arrow(2)) of a zero-field-split, high-spin d(4)-d(4) dimer in its actual crystallographic geometry, using numerical techniques. The hydroxide bridge supports a relatively strong antiferromagnetic coupling (2J = -71.0 +/- 0.4 cm(-1)) between two zero-field-split (D = -8 +/- 2 cm(-1)) manganese(III) ions. The synthesis and characterization of one monomeric precursor, [Mn(OEP)(H2O)]ClO4 . H2O, is also reported. This species is a simple paramagnet. The crystal structure analysis shows it to be a five-coordinate, high-spin manganese(III) complex. Crystal data: {[Mn(OEP)](2)(OH)}ClO4 . 3CH(2)Cl(2), a = 14.791(4) Angstrom, b = 14.895(2) Angstrom, c = 18.634(4) Angstrom, alpha = 69.79(2)degrees, beta = 89.24(2)degrees, gamma = 88.86(2)degrees, triclinic, space group , V = 3851.7(14) Angstrom(3), Z = 2, R(1) = 0.0655 for 15 643 observed data based on F-o greater than or equal to 4.0 sigma(F-o), wR(2) = 0.1631 for 19 422 total unique data, least-squares refinement on F-2 using all data; [Mn(OEP)(H2O)]ClO4 . H2O, a = 12.800(1) Angstrom, b = 13.506(4) Angstrom, c = 13.355(7) Angstrom, alpha = 64.80 (2)degrees, beta = 62.36(3)degrees, gamma = 85.67(3)degrees, triclinic, space group , V = 1829.1(11) Angstrom(3), Z = 2, R(1) = 0.0754 for 5715 observed data based on F-o greater than or equal to 4.0 sigma(F-o), wR(2) = 0.2210 for 8891 total unique data, least-squares refinement on F-2 using all data.

  DOI：

  10.1021/ic00122a020
• 作为产物：
  描述：

  高氯酸 、 2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物 以 高氯酸 、 二氯甲烷 为溶剂， 生成 (2,3,7,8,12,13,17,18-octaethylporphinato)perchloratomanganese(III)
  参考文献：
  名称：

  A Novel Dimanganese(III) Complex with a Single Hydroxo Bridge. Syntheses, Structures, and Magnetic Susceptibilities of (.mu.-Hydroxo)bis((octaethylporphinato)manganese(III)) Perchlorate and a Monomeric Precursor, Aquo(octaethylporphinato)manganese(III) Perchlorate

  摘要：

  The synthesis and structural and magnetic characterization of a dimanganese(III) complex with a novel, single, hydroxo bridge is described. The complex, (mu-hydroxo)bis((octaethylporphinato)manganese(III)) perchlorate, can be prepared by protonation of an ore-bridged manganese complex or, more reliably, by hydrolysis of monomeric manganese(III) octaethylporphyrinates. The crystal and molecular structure has been solved using X-ray diffraction data collected with an area detector. The two five-coordinate manganese(III) ions in {[Mn(OEP)](2)(OH)}ClO4 are bridged by a single hydroxo ligand with an average Mn-O distance of 2.011 Angstrom and a Mn-O(H)-Mn bridge angle of 152.73 degrees. The average Mn-N-p distance is 2.006 Angstrom. The two porphyrin rings are crowded against each other and are hence canted with a dihedral angle of 12.7 degrees. An additional distortion from ring crowding occurs in the coordination angles O-Mn-N-p at one manganese(III) ion but not at the other. The magnetic susceptibility of the hydroxo-bridged complex has been measured over the temperature range 2-300 K. The observed behavior is typical of an exchange-coupled binuclear complex. The data have been fit to the total spin Hamiltonian (H-tot = H(1) + H(2) - 2J (S) over right arrow(1) .(S) over right arrow(2)) of a zero-field-split, high-spin d(4)-d(4) dimer in its actual crystallographic geometry, using numerical techniques. The hydroxide bridge supports a relatively strong antiferromagnetic coupling (2J = -71.0 +/- 0.4 cm(-1)) between two zero-field-split (D = -8 +/- 2 cm(-1)) manganese(III) ions. The synthesis and characterization of one monomeric precursor, [Mn(OEP)(H2O)]ClO4 . H2O, is also reported. This species is a simple paramagnet. The crystal structure analysis shows it to be a five-coordinate, high-spin manganese(III) complex. Crystal data: {[Mn(OEP)](2)(OH)}ClO4 . 3CH(2)Cl(2), a = 14.791(4) Angstrom, b = 14.895(2) Angstrom, c = 18.634(4) Angstrom, alpha = 69.79(2)degrees, beta = 89.24(2)degrees, gamma = 88.86(2)degrees, triclinic, space group , V = 3851.7(14) Angstrom(3), Z = 2, R(1) = 0.0655 for 15 643 observed data based on F-o greater than or equal to 4.0 sigma(F-o), wR(2) = 0.1631 for 19 422 total unique data, least-squares refinement on F-2 using all data; [Mn(OEP)(H2O)]ClO4 . H2O, a = 12.800(1) Angstrom, b = 13.506(4) Angstrom, c = 13.355(7) Angstrom, alpha = 64.80 (2)degrees, beta = 62.36(3)degrees, gamma = 85.67(3)degrees, triclinic, space group , V = 1829.1(11) Angstrom(3), Z = 2, R(1) = 0.0754 for 5715 observed data based on F-o greater than or equal to 4.0 sigma(F-o), wR(2) = 0.2210 for 8891 total unique data, least-squares refinement on F-2 using all data.

  DOI：

  10.1021/ic00122a020

文献信息

• Synthesis, characterization and solid state molecular structures of five- and six-coordinate primary amide manganese porphyrin complexes
  作者：Nan Xu、Alexander W. Bevak、Bernadette R. Armstrong、Douglas R. Powell

  DOI：10.1016/j.poly.2016.10.022

  日期：2017.5

  Abstract We report the synthesis and characterization of a number of primary amide manganese porphyrins from the reactions of the cationic [(por)Mn(THF)2]ClO4 (por = tetraphenylporphyrin dianion (TPP), tetra(p-chlorophenyl) porphyrin dianion (T(p-Cl)PP) and [(OEP)Mn]ClO4 (OEP = octaethylporphyrin dianion) precursors with excess acrylamide or acetamide. Two six-coordinate [(por)Mn(O C(NH2)CH CH2)2]ClO4

  摘要我们报告了阳离子[[por] Mn（THF）2] ClO4（por =四苯基卟啉二价阴离子（TPP），四（对氯苯基）卟啉二价阴离子（）的反应合成了许多伯酰胺锰卟啉的合成和表征。 T（p-Cl）PP）和[（OEP）Mn] （OEP =八乙基卟啉二价阴离子）前体，带有过量的丙烯酰胺或乙酰胺。两个六配位[[por）Mn（OC（NH2）CH CH2）2] （ por = TPP（1）T（p-Cl）PP（2））配合物和一种五配位[（OEP）Mn（OC（NH2）CH3）] （4）配合物已通过X射线晶体学进行了结构表征。已经确定了这些配合物中伯酰胺配体的唯一O结合模式。[（por）Mn（OC（NH2）CH ）2] 配合物的氧化还原行为已通过循环伏安法进行了研究，结果表明-为两个配合物定义了可逆的还原对。
• (2,3,7,8,12,13,17,18-Octaethylporphinato)perchloratomanganese(III)
  作者：B. Cheng、W. R. Scheidt

  DOI：10.1107/s0108270194013181

  日期：1995.5.15

  The crystal structure of [Mn(OEP)(OClO3)] (where OEP = C36H44N4) has been determined. The axial Mn-O bond length is 2.183 (2) Angstrom and the equatorial Mn-N-p bond lengths have an average value of 2.000 (5) Angstrom. The molecules form weak dimers in the solid state with interring distances of 3.49 Angstrom and a lateral shift of 3.27 Angstrom. The compound is found to be isomorphous with the iron derivative [Fe(OEP)(OClO3)]. A brief comparison of the structural parameters for the two molecules is given.