[Mn^III(O₂)(N-methyl-N,N0,N0-tris(2-pyridylmethyl)ethane-1,2-diamine)]+ | 934373-81-6

• 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: [Mn^III(O₂)(N-methyl-N,N0,N0-tris(2-pyridylmethyl)ethane-1,2-diamine)]+
• 英文别名: [Mn^III(O₂)(mL₅²)]+；[manganese(III)(peroxido)(N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-diaminoethane)](1+)；[(N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine)MnO2](1+)；[Mn(III)O2(bpmen)](1+)
• CAS: 934373-81-6
• 化学式: C₂₁H₂₅N₅*Mn*O₂
• 分子量: 434.4
• InChiKey: SCTIDBVXNZBYCZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.63
• 重原子数：
  29.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  91.27
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为产物：
  描述：

  N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine 以 二甲基亚砜 、 乙腈 为溶剂， 生成 [Mn^III(O₂)(N-methyl-N,N0,N0-tris(2-pyridylmethyl)ethane-1,2-diamine)]+
  参考文献：
  名称：

  Reactivity of Mn^II with Superoxide. Evidence for a [Mn^IIIOO]⁺ Unit by Low-Temperature Spectroscopies

  摘要：

  Manganese superoxide dismutase cycles between the Mn-III and Mn-II states to produce oxygen and hydrogen peroxide from superoxide. The formation of an adduct has been suggested, but its nature remains questionable because both [(MnOO-)-O-II] and [(MnOO2-)-O-III] redox states have been proposed. Study of the reactivity of superoxide with manganese complexes is of current interest. The reaction of [(L)Mn-II](2+) [L = N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine] with potassium superoxide has been investigated at low temperature in an anhydrous solvent using various techniques. Upon the addition of ca. 2 equiv of potassium superoxide, the [(L)Mn-II](2+) colorless solution turned blue and the UV-vis spectrum displayed a band at 590 nm (165 M-1 cm(-1)) and a shoulder at 430 nm (100 M-1 cm(-1)). Electrospray ionization mass spectrometry showed a peak (m/z = 434.1) assigned to [(L)MnO2](+). The X-band electron paramagnetic resonance spectrum parallel mode displayed a six-line signal separated by 6.6 mT and centered at 86 mT (g = 8.1). These results support the formation of an [(MnOO)-O-III](+) adduct.

  DOI：

  10.1021/ic062063+

文献信息

• Electrochemical formation of MnIII-peroxo complexes supported by pentadentate amino pyridine and imidazole ligands
  作者：Sanae El Ghachtouli、H. Y. Vincent Ching、Benedikt Lassalle-Kaiser、Régis Guillot、Domenick F. Leto、Swarup Chattopadhyay、Timothy A. Jackson、Pierre Dorlet、Elodie Anxolabéhère-Mallart

  DOI：10.1039/c3cc41300d

  日期：——

  A novel and efficient method for preparing [Mn(III)(O2)(L)](+) complexes using electrochemically generated superoxide is reported, with the reaction probed by low temperature electronic absorption and electron paramagnetic resonance spectroscopic techniques.

  报道了一种利用电化学产生的超氧化物制备[Mn（III）（O2）（L）]（+）配合物的新颖有效的方法，该反应通过低温电子吸收和电子顺磁共振光谱技术进行探测。
• Reactivity of an Aminopyridine [LMn^II]²⁺ Complex with H₂O₂. Detection of Intermediates at Low Temperature
  作者：Sihem Groni、Pierre Dorlet、Guillaume Blain、Sophie Bourcier、Régis Guillot、Elodie Anxolabéhère-Mallart

  DOI：10.1021/ic702238z

  日期：2008.4.1

  nonanhydrous medium the fate of the reaction mixture solution is the formation of the di-mu-oxo mixed-valent Mn(III)Mn(IV) dinuclear complex. In acidic medium the building of the oxo bridges is avoided and the reaction mixture evolves toward oxidation of the ligand L. This reaction route offers new opportunities for the study of oxidation reactivity of Mn (hydro)peroxo complexes.

  在本工作中，我们报道了[LMnII] 2+对乙腈溶液中过氧化氢（H2O2）添加的反应性，其中L是五齿的聚吡啶配体。过氧配合物的形成通过使用平行和垂直模式检测的低温紫外-可见光谱，ESI质谱和EPR光谱来证明。研究了介质（碱度，水含量）对各种物种形成的影响。在碱性无水介质中，反应混合物溶液的结局是二-木氧基混合价Mn（III）Mn（IV）双核配合物的形成。在酸性介质中，避免了氧代桥的建立，并且反应混合物向配体L的氧化方向发展。该反应路线为研究Mn（氢）过氧配合物的氧化反应性提供了新的机会。
• Geometric and Electronic Structures of Peroxomanganese(III) Complexes Supported by Pentadentate Amino-Pyridine and -Imidazole Ligands
  作者：Robert A. Geiger、Domenick F. Leto、Swarup Chattopadhyay、Pierre Dorlet、Elodie Anxolabéhère-Mallart、Timothy A. Jackson

  DOI：10.1021/ic201168j

  日期：2011.10.17

  Three peroxomanganese(III) complexes [MnIII(O2)(mL52)]+, [MnIII(O2)(imL52)]+, and [MnIII(O2)(N4py)]+ supported by pentadentate ligands (mL52 = N-methyl-N,N′,N′-tris(2-pyridylmethyl)ethane-1,2-diamine, imL52 = N-methyl-N,N′,N′-tris((1-methyl-4-imidazolyl)methyl)ethane-1,2-diamine, and N4py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) were generated by treating Mn(II) precursors with H2O2

  [锰三个peroxomanganese（III）配合物III（O 2）（毫升5 2）] +，[锰III（O 2）（IML 5 2）] +和[锰III（O 2）（N4py）] +支持通过五齿配体（mL 5 2 = N-甲基-N，N '，N'-三（2-吡啶基甲基）乙烷-1,2-二胺，imL 5 2 = N-甲基-N，N '，N′-三（（1-甲基-4-咪唑基）甲基）乙烷-1，2-二胺，且N4py ＝N，生成N-双（2-吡啶基甲基）-N-双（2-吡啶基）甲胺）用H 2 O 2或KO 2处理Mn（II）前体。电子吸收，磁圆二色​​性（MCD）和可变温度，可变场MCD数据表明，这些配合物具有非常相似的电子跃迁能和基态零场分裂参数，表明配位几何几乎相同。因为在过氧的不确定性（侧上η 2与端部上η 1）和配体（五齿与四齿）结合模式，密度泛函理论（DFT）计算用于区分三种可能的结构：五齿配体与（i）侧面过氧
• [Mn(tmc)(O2)]+: A Side-On Peroxido Manganese(III) Complex Bearing a Non-Heme Ligand
  作者：Mi Sook Seo、Ja Young Kim、Jamespandi Annaraj、Youngmee Kim、Yong-Min Lee、Sung-Jin Kim、Jinheung Kim、Wonwoo Nam

  DOI：10.1002/anie.200603414

  日期：2007.1.8