MnIIIMnIII(2-OH-3,5-diClSalpn)2 | 150378-61-3

• 英文名称: MnIIIMnIII(2-OH-3,5-diClSalpn)2
• 英文别名: [Mn(III)2(1,3-bis(3,5-dichlorosalicylideneamino)-2-propoxide)2]；Mn^IIIMn^III(2-OH-3,5-diClSalpn)₂
• CAS: 150378-61-3
• 化学式: C₃₄H₂₂Cl₈Mn₂N₄O₆
• 分子量: 976.072
• InChiKey: TURLZRDUWFLFGP-RFRKDEBGSA-J

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：

  MnIIIMnIII(2-OH-3,5-diClSalpn)2 在 thianthryl perchlorate 作用下， 以 乙腈 为溶剂， 生成 [Mn(III)Mn(IV)(1,3-bis(3,5-dichlorosalicylideneamino)-2-propoxide)2](ClO4)
  参考文献：
  名称：

  [Mn（2）（2-OHsalpn）（2）]（2-，-，0，+）系统：包含四个不同氧化态的第一个结构表征的双核锰系列的合成，结构，光谱和磁性。

  摘要：

  配合物系列[Mn（2）（2-OH（Xsal）pn）（2）]（2-，-，0，+）[其中2-OH（Xsal）pn表示取代的苯环衍生物（X = H，5-Cl，3,5-Cl（2），5-NO（2））的1,3-双（水杨亚氨基）-2-丙醇]允许对以下化合物进行第一个详细的结构，磁性和光谱研究一系列配合物，它们是锰过氧化氢酶最活跃的功能模型。该系列的每个氧化态的代表实例（模仿了酶反应化学的所有已知氧化态）已经在晶体学上进行了表征。本文呈现的分子被描述为对称衍生物，因为它们与两个跨越两个Mn离子的配体形成二聚体，并且在桥接金属的配体主链上形成醇盐。四个结构中Mn-Mn分离的变化为0。11Å[Mn（II）-Mn（II）= 3.33Å; Mn（II）-Mn（III）= 3.25Å; Mn（III）-Mn（III）= 3.36Å; Mn（III）-Mn（IV）= 3.25Å]，表明基本核结构高度不变。但是，可以在

  DOI：

  10.1021/ic970140i
• 作为产物：
  描述：

  Na2[Mn(II)2(1,3-bis(3,5-dichlorosalicylideneamino)-2-propoxide)2] 在 air 作用下， 以 二氯甲烷 为溶剂， 生成 MnIIIMnIII(2-OH-3,5-diClSalpn)2
  参考文献：
  名称：

  [Mn（2）（2-OHsalpn）（2）]（2-，-，0，+）系统：包含四个不同氧化态的第一个结构表征的双核锰系列的合成，结构，光谱和磁性。

  摘要：

  配合物系列[Mn（2）（2-OH（Xsal）pn）（2）]（2-，-，0，+）[其中2-OH（Xsal）pn表示取代的苯环衍生物（X = H，5-Cl，3,5-Cl（2），5-NO（2））的1,3-双（水杨亚氨基）-2-丙醇]允许对以下化合物进行第一个详细的结构，磁性和光谱研究一系列配合物，它们是锰过氧化氢酶最活跃的功能模型。该系列的每个氧化态的代表实例（模仿了酶反应化学的所有已知氧化态）已经在晶体学上进行了表征。本文呈现的分子被描述为对称衍生物，因为它们与两个跨越两个Mn离子的配体形成二聚体，并且在桥接金属的配体主链上形成醇盐。四个结构中Mn-Mn分离的变化为0。11Å[Mn（II）-Mn（II）= 3.33Å; Mn（II）-Mn（III）= 3.25Å; Mn（III）-Mn（III）= 3.36Å; Mn（III）-Mn（IV）= 3.25Å]，表明基本核结构高度不变。但是，可以在

  DOI：

  10.1021/ic970140i

文献信息

• Thermodynamic Viability of Hydrogen Atom Transfer from Water Coordinated to the Oxygen-Evolving Complex of Photosystem II
  作者：M. Tyler Caudle、Vincent L. Pecoraro

  DOI：10.1021/ja9641158

  日期：1997.4.1

  the role of proton transfer in S-state advancement is understanding of proton-coupled electron transfer effects in model manganese complexes in high oxidation states. In an initial attempt to address this hypothesis through biologically relevant model complexes, our group has recently measured the homolytic bond dissociation energy (BDEsub OH}) for a bridging hydroxide ligand in Mnsup III}Mnsup

  任何评估质子转移在 S 态进展中的作用的关键是了解高氧化态锰配合物中的质子耦合电子转移效应。在通过生物相关模型复合物解决这一假设的初步尝试中，我们的小组最近测量了 Mnsup III}Mnsup IV}(mu }-O, mu}-OH)(salpn)sub 2} 二聚体（salpn = 1,3-双（水杨基氨基）丙烷）为 77-(+-}3) kcal/mol。此处提供的数据表明，直接与高价 Mn 配合物结合的水的 BDEsub OH} 比简单的大量水的 BDEsub OH} 要小得多。Ysub z}center_dot} 的结构和功能的最新数据与这里报道的模型研究相结合，为氢原子从结扎水转移到 Ysub z}center_dot} 提供了一个间接但令人信服的案例，作为OEC中逐步簇氧化的机制。16 个参考文献，2 个无花果，2 个标签。
• Mechanism for the Homolytic Cleavage of Alkyl Hydroperoxides by the Manganese(III) Dimer Mn^III₂(2-OHsalpn)₂
  作者：M. Tyler Caudle、Pamela Riggs-Gelasco、Andrew K. Gelasco、James E. Penner-Hahn、Vincent L. Pecoraro

  DOI：10.1021/ic951462u

  日期：1996.1.1

  The oxidation of Mn-2(III)(2-OHsalpn)(2), 1 (2-OHsalpn = 1,3-bis (salicylideneamino)-2-propanol), with tert-butyl hydroperoxide was studied in organic media. A one-electron reaction occurs resulting in initial formation of the oxidized (MnMnIV)-Mn-III(2-OHsalpn)(2)OH species 2 and a tert-butoxy radical. The (MnMnIV)-Mn-III(2-OHsalpn)(2)OH complex can be readily protonated to yield (MnMnIV)-Mn-III(2-OHsalpn)(2)(+). Upon addition of excess tert-butyl hydroperoxide, singlet dioxygen is evolved in an exothermic reaction indicative of radical-induced disproportionation of the hydroperoxide. In the presence of a radical scavenger, the oxygen evolution is strongly attenuated. This system was observed to oxygenate cyclohexene to yield 2-cyclohexen-1-one, 2-cyclohexen-1-ol, and traces of cyclohexene oxide. Cumene is oxygenated to 2-phenyl-2-propanol and acetophenone, and cyclohexane is oxygenated to cyclohexanone and cyclohexanol. However, O-18-labeling experiments show that the oxygen in the products results exclusively from reactions with aerobic dioxygen and not from the tert-butyl hydroperoxide oxidant. These results indicate that oxygenation occurs by radical-initiated aerobic autoxidation and not via oxo transfer from a high-valent manganese oxo species. 2 was studied by UV-vis, IR, NMR, EXAFS, XANES, and EPR spectroscopies, which support the assignment of a dinuclear manganese(III/IV) terminal hydroxo structure. 2 was also formed by the direct reaction of (MnMnIV)-Mn-III(2-OHsalpn)(2)(+) with OH-, further supporting the description of 2 as having a terminal hydroxide ligand. The kinetics of its formation from 1 and tert-butyl hydroperoxide were examined and found to be first-order in peroxide. Titration experiments confirm that 1 equiv of peroxide is required to convert 1 to 2, supporting the conclusion that the peroxide undergoes a one-electron reduction. This system demonstrates that oxy radicals formed from homolytic one-electron cleavage of a peroxide by a manganese(III) complex can give small amounts of olefin oxidation species (i.e. epoxides) normally considered evidence for high-valent manganese oxo-transfer chemistry. It therefore underscores the need to test any system for which high-valent metal oxo transfer is proposed to occur using rigorous oxygen-labeling experiments to determine the source of oxygen.
• Use of the mechanistic probe 2-methyl-1-phenylpropan-2-yl hydroperoxide (MPPH) to discriminate between the formation of MnIVMnIV(OH) and MnIVMnVO species
  作者：Fangting Yu、Vincent L. Pecoraro

  DOI：10.1016/j.poly.2013.02.074

  日期：2013.11

  High-valent Mn species are key intermediates in the oxygen evolving complex in photosystem II. In some mechanisms, the Mn-V O moiety is proposed to be a critical species at the final step of oxygen production. This work reports the use of a mechanistic probe 2-methyl-1-phenylpropan-2-yl hydroperoxide (MPPH) to distinguish the formation of (MnMnIV)-Mn-IV(OH) and (MnMnV)-Mn-IV O species. We demonstrate that a dimeric Mn complex [(MnMnIV)-Mn-III(2-OH-3,5-diClsalpn)](+) reacts with MPPH, leading to the production of the O-O bond heterolysis product. In this process, the Mn complex transforms into a transient (MnMnV)-Mn-IV O species, which undergoes comproportionation rapidly. (C) 2013 Elsevier Ltd. All rights reserved.