2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物 | 28265-17-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 中文名称: 2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物
• 中文别名: 禾大壮；环草丹；杀草丹；禾草敌
• 英文名称: (chloro)(2,3,7,8,12,13,17,18-octaethylporphyrinato)manganese(III)
• 英文别名: (chloro)(2,3,7,8,12,13,17,18-octaethylporphinato)manganese(III)；[Mn(OEP)Cl]；(Cl)Mn(III) 2,3,7,8,12,13,17,18-octaethylporphyrinate；(Cl)MnOEP；(2,3,7,8,12,13,17,18-octaethylporphynato)chloromanganese(III)；(chloro)(octaethylporphinato)manganese(III)；chloromanganese(III) octaethylporphyrinate；ClMn(III)(octaethylporphyrin)；(Cl)Mn(octaethylporphine-2H)；[MnCl(octaethylporphine)]
• CAS: 28265-17-0
• 化学式: C₃₆H₄₄ClMnN₄
• 分子量: 623.163
• InChiKey: ZMCDJCAIDCCCKY-YAJYDHHFSA-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：
  None
• 氢受体数：
  None

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物 在 四丁基氢氧化铵 作用下， 以 乙腈 为溶剂， 生成 ClMn(IV)O(octaethylporphyrin)
  参考文献：
  名称：

  通过共振拉曼光谱和红外光谱鉴定的氧锰 (IV) 卟啉。弱键和半填充 t2g 子壳的稳定性

  摘要：

  在通过 ClMn/sup III/TMP 电氧化制备的 Mn/sup IV/卟啉的共振拉曼 (RR) 和红外 (IR) 光谱中，Mn/sup IV/-O 的伸缩频率确定为 754 cm/sup -1/。 TMP = 四甲基卟啉）、ClMn/sup III/TPP（TPP = 四苯基卟啉）和 ClMn/sup III/OEP（OEP = 八乙基卟啉）在 CH/sub 3/CN 中含有四丁基氢氧化铵（TBA（OH））。该振动带在这些条件下建立 oxo-Mn/sup IV/ 键形成，并显示键异常弱。当氧化在含有 TBA(OH) 的 CH/sub 2/Cl/sub 2/ 中进行时，或当 ClMn/sup III/TMPyP（TMPyP = 四（甲基吡啶）卟啉）在 1 M NaOH 水溶液中电氧化时，Mn -O 拉伸带可见于 711 cm/sup /minus/1/。该带与反式 OH/sup /minus//

  DOI：

  10.1021/ja00221a010
• 作为产物：
  描述：

  [(octaethylporphyrinato)manganese(III)]2O hydrate 在 chlorocarbon solvents 作用下， 以 not given 为溶剂， 生成 2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物
  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
• 作为试剂：
  描述：

  双氧水 在 2,3,7,8,12,13,17,18-八乙基-21H,23H-卟吩锰(III)氯化物 氢氧化钾 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 氧气
  参考文献：
  名称：

  Disproportionation of hydrogen peroxide in the presence of Mn(III) complexes with various porphyrins and acid anions

  摘要：

  The kinetics of homogeneous decomposition of H2O2 in the presence of Mn(IIII) complexes with octaethylporphine or meso-phenyloctaethylporphines and acid anions Cl-, AcO-, and SCN- was studied by volumetry. The ionic-molecular mechanism of the transformation, involving reversible coordination of the H2O2 molecule, its irreversible decomposition with the release of H2O and removal of two electrons from the metal porphyrin, reversible coordination of the second peroxide molecule in the form of HO2-, and slow irreversible reduction of the catalyst with the release of O-2 and H2O was substantiated by electronic absorption spectra. The catalytic activity of Mn(III) porphyrin complexes is independent of the acid anion present as extra ligand, but depends on the structure of the porphyrin ligand, which can be used for controlling the catalytic activity. Unsymmetrical (chloro)(monophenyloctaethylporphinato)manganese(III) is the most active; it increases the rate of O-2 evolution by a factor of 2 at the peroxide : catalyst molar ratio of (3 x 10(5)):1.

  DOI：

  10.1134/s1070363206090210

文献信息

• Effects of porphyrin deformation on the 13C and¹H NMR chemical shifts in high-spin five- and six-coordinate manganese(III) porphyrin complexes
  作者：Akira Ikezaki、Mikio Nakamura

  DOI：10.1142/s1088424616500085

  日期：2016.1

  effect of porphyrin deformation on the [Formula: see text]C and 1H NMR chemical shifts, both five- and six-coordinate high-spin (S [Formula: see text] 2) Mn(III) complexes such as Mn(Por)Cl and [Mn(Por)(CD3OD)2]Cl have been prepared, where Por is a porphyrin dianion such as TPP, OMTPP, and T[Formula: see text]PrP. Molecular structures of five-coordinate Mn(OMTPP)Cl and Mn(TiPrP)Cl have been determined

  作为我们研究的延伸，以揭示卟啉变形对[公式：见正文]C和1H NMR 化学位移，五配位和六配位高自旋（S [公式：见正文] 2）Mn(III) 配合物，例如 Mn(Por)Cl 和 [Mn(Por)(CD3外径)2]Cl 已制备，其中 Por 是卟啉双阴离子，例如 TPP、OMTPP 和 T[公式：见正文]PrP。五配位Mn(OMTPP)Cl和Mn(T)的分子结构一世PrP)Cl 已通过 X 射线晶体学分析确定。正如所料，Mn(OMTPP)Cl 和 Mn(T一世PrP)Cl 分别表现出高度鞍状和高度褶皱的卟啉核心。[分子式：见正文]C NMR谱表明，这些配合物一般在低场位置表现出[分子式：见文字]-吡咯信号和[分子式：见文字]-吡咯和。高场位置的中观信号。结果表明，Mn(III)-N 的自旋极化磷存在于所有高自旋 Mn(III) 配合物中的 σ 键是决定卟啉碳信号化学位移的主要因素 (Cheng
• Meso-nitro substitution as a means of Mn-octaethylporphyrin redox state controlling
  作者：Olga A. Dmitrieva、Natalya V. Chizhova、Mariya V. Tesakova、Vladimir I. Parfenyuk、Nugzar Zh. Mamardashvili

  DOI：10.1016/j.jorganchem.2021.121790

  日期：2021.5

  and metal exchange of their cadmium complexes with manganese (II) chloride in dimethylformamide was carried out to find the optimal conditions for the synthesis of Mn(II, III)-porphyrins. The obtained compounds were identified by UV-vis, 1H NMR spectroscopy and mass spectrometry. The structural parameters of the synthesized compounds were calculated by the DFT method and their NBO analysis was carried

  5-一硝基2,3,7,8,12,13,17,18-八乙基卟啉，5,15-二硝基-八乙基卟啉，5,10,15的Mn（II，III）和Cd（II）络合物-trinitro-2,3,7,8,12,13,17,18-八乙基卟啉和5,10,15,20-tetranitro-2,3,7,8,12,13,17,17,18-octaethylporphyrin已被综合和确定。比较了相应的卟啉配体与氯化锰（II）的配位反应，以及镉配合物与氯化锰（II）在二甲基甲酰胺中的金属交换，从而找到了合成Mn（II，III）的最佳条件。 ）-卟啉。所获得的化合物通过紫外可见分光光度法鉴定11 H NMR光谱和质谱。用DFT法计算了合成化合物的结构参数，并进行了NBO分析。用循环伏安法研究了合成的锰配合物的电化学性能。结果表明，硝基取代决定了Mn-卟啉的氧化还原状态。
• Synthesis and properties of a new (octaethylporphyrinato)-manganese(III)–pyridinyl-substituted pyrrolidinofullerene dyad
  作者：E. N. Ovchenkova、N. G. Bichan、T. N. Lomova

  DOI：10.1134/s1070428016100213

  日期：2016.10

  activity. Preliminarily, the reaction of manganese(III) porphyrin with pyridine has been studied. The donor–acceptor dyads are formed either instantaneously and reversibly (pyridine) or slowly and irreversibly (substituted fullerene). In both cases, the reaction is a one-step process for which thermodynamic and kinetic parameters have been determined. The results can be used to optimize conditions for the

  由2'-（吡啶-4-基）-5'-（吡啶-2-基）-1'-（吡啶-3-基甲基）-2'，5'-二氢- 1' ħ吡咯并[3'，4'：1,9]（C 60 -我 ħ定量研究了具有轴向氯化物配体的）[5,6]富勒烯和（2,3,7,8,12,13,17,17,18-八乙基卟啉）锰（III），目的是获得具有生物学特性的超分子活动。初步研究了锰（III）卟啉与吡啶的反应。供体-受体二联体既可以瞬时可逆地形成（吡啶），也可以缓慢且不可逆地形成（取代的富勒烯）。在两种情况下，反应都是一步法，已确定了热力学和动力学参数。结果可用于优化合成卟啉-富勒烯二元组的条件。通过光谱数据和稳定性常数来表征所获得的二元组。
• Nitrogen Atom Transfer between Manganese Complexes of Salen, Porphyrin, and Corrole and Characterization of a (Nitrido)manganese(VI) Corrole
  作者：Galina Golubkov、Zeev Gross

  DOI：10.1021/ja043683h

  日期：2005.3.1

  atom transfer reactions from (nitrido)manganese(V) salen to manganese(III) complexes of porphyrins and corroles revealed that stabilization of the [Mn(N)]2+ moiety is in the order of corrole > porphyrin > salen. The first kinetic examination of this quite fundamental reaction exposed a large solvent effect on both the enthalpy and entropy activation energies. Oxidation of the (nitrido)manganese(V) corroles

  从（硝基）锰（V）salen到卟啉和钴的锰（III）配合物的完全氮原子转移反应的研究表明，[Mn（N）]2+部分的稳定化顺序为：卟啉>卟啉>萨伦。这个非常基本的反应的第一次动力学检查揭示了对焓和熵活化能的巨大溶剂效应。（亚氮基）锰（V）氧化导致第一个（亚氮基）锰（VI）配合物由四吡咯配体配位。
• The preparation of nitridomanganese and nitridochromium macrocyclic complexes by complete intermetal nitrogen atom transfer from nitridomanganese octaethylporphyrin
  作者：Frank L. Neely、Lawrence A. Bottomley

  DOI：10.1016/s0020-1693(00)80751-3

  日期：1992.2

  Atom transfer reactions involve the net transfer of an atom and one or more electrons from a donor molecule to an acceptor [l]. Over the past two decades, metal-centered oxygen atom transfer reactions have been intensively studied. Oxygen atom transfer from M=O containing donor complexes to olefins, paraffins and other substrates has been achieved and a consistent mechanistic picture is beginning to

  原子转移反应涉及原子和一个或多个电子从供体分子到受体的净转移[1]。在过去的二十年中，对以金属为中心的氧原子转移反应进行了深入研究。氧原子已从含M = O的供体配合物转移至烯烃，石蜡和其他底物，并且已经出现了一致的机理图[2]。相对较少的非氧杂原子转移的例子已有报道。在大多数情况下，这种转移是不完全的，即原子被供体金属和受体基团共享。霍尔姆已经描述了这种类型的配合物作为部分原子转移的例子[1]。