[Mn(III)(TMpyP)(H2O)OH](4+) | 89043-42-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: [Mn(III)(TMpyP)(H2O)OH](4+)
• 英文别名: (tetra-(N-methylpyridyl)porphyrinato)manganese(III)(4+)；[Mn(III)(meso-tetra(N-methylpyridinium-4-yl)porphyrin)(OH)(OH₂)]⁴⁺；[Mn(TMPyP)(OH)(OH₂)]⁴⁺；[Mn(III)(TMPyP)(H2O)(OH)](4+)
• CAS: 89043-42-5
• 化学式: C₄₄H₃₉MnN₈O₂
• 分子量: 766.784
• InChiKey: RPMMDUGLPPDFTI-UHFFFAOYSA-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

反应信息

• 作为反应物：
  描述：

  [Mn(III)(TMpyP)(H2O)OH](4+) 在 异丙醇 作用下， 以 水 为溶剂， 以>99的产率得到
  参考文献：
  名称：

  锰卟啉在水溶液中的氧化还原反应。稳态和脉冲辐射分解分光光度法研究

  摘要：

  DOI：

  10.1021/j150652a027
• 作为产物：
  描述：

  oxo-aquo-Mn(V)TM-4-pyridyl 在 维生素 C 作用下， 以 水 为溶剂， 生成 [Mn(III)(TMpyP)(H2O)OH](4+)
  参考文献：
  名称：

  Manganese Porphyrins as Redox-Coupled Peroxynitrite Reductases

  摘要：

  Superoxide (O-2.(-)) and peroxynitrite (ONOO-) have been implicated in many pathophysiological conditions. To develop novel catalysts that have both ONOO- decomposition and O-2.(-) dismutase activity, and to understand the mechanisms of these processes, we have explored the reactivity of 5,10, 15,20-tetrakis(N-methyl-4'-pyridyl)porphinatomanganese [Mn(III)TMPyP] toward ONOO- and O-2.(-). The reaction of Mn(III)TMPyP with ONOO- to generate an oxomanganese(IV) porphyrin species [(oxoMn(IV)] is fast, but Mn(III)TMPyP is not catalytic for ONOO- decomposition because of the slow reduction of oxoMn(IV) back to the Mn(III) oxidation state. However, biological antioxidants such as ascorbate, glutathione, and Trolox rapidly turn over the catalytic cycle by reducing oxoMn(IV). Thus, Mn(III)TMPyP becomes an efficient peroxynitrite reductase when coupled with ascorbate, glutathione, and Trolox (k(c) approximate to 2 x 10(6) M-1 s(-1)), though the direct reactions of ONOO- with these biological antioxidants are slow (88 M-1 s(-1), 5.8 x 10(2) M-1 s(-1) and 33 M-1 s(-1), respectively). Mn(In)TMPyP is known to catalyze the dismutation of O-2.(-), and using stopped-flow spectrophotometry, the rate of Mn(III)TMPyP-catalyzed dismutation has been measured directly (k(c)= 1.1 x 10(7) M-1 s(-1)). Further, O-2.(-), like the biological antioxidants, rapidly reduces oxoMn(IV) to the Mn(III) oxidation state (k approximate to 10(8) M-1 s(-1)), transforming Mn(III)TMPyP into a O-2.(-)-coupled ONOO- reductase. Under conditions of oxidative stress and reduced antioxidant levels, Mn(III)TMPyP may deplete O-2.(-) primarily as a function of its ONOO- reductase activity, and not through its O-2.(-) dismutase activity.

  DOI：

  10.1021/ja9801036
• 作为试剂：
  描述：

  亚硝酸氧盐 在 [Mn(III)(TMpyP)(H2O)OH](4+) 作用下， 以 水 为溶剂， 生成 二氧化氮
  参考文献：
  名称：

  Manganese Porphyrins as Redox-Coupled Peroxynitrite Reductases

  摘要：

  Superoxide (O-2.(-)) and peroxynitrite (ONOO-) have been implicated in many pathophysiological conditions. To develop novel catalysts that have both ONOO- decomposition and O-2.(-) dismutase activity, and to understand the mechanisms of these processes, we have explored the reactivity of 5,10, 15,20-tetrakis(N-methyl-4'-pyridyl)porphinatomanganese [Mn(III)TMPyP] toward ONOO- and O-2.(-). The reaction of Mn(III)TMPyP with ONOO- to generate an oxomanganese(IV) porphyrin species [(oxoMn(IV)] is fast, but Mn(III)TMPyP is not catalytic for ONOO- decomposition because of the slow reduction of oxoMn(IV) back to the Mn(III) oxidation state. However, biological antioxidants such as ascorbate, glutathione, and Trolox rapidly turn over the catalytic cycle by reducing oxoMn(IV). Thus, Mn(III)TMPyP becomes an efficient peroxynitrite reductase when coupled with ascorbate, glutathione, and Trolox (k(c) approximate to 2 x 10(6) M-1 s(-1)), though the direct reactions of ONOO- with these biological antioxidants are slow (88 M-1 s(-1), 5.8 x 10(2) M-1 s(-1) and 33 M-1 s(-1), respectively). Mn(In)TMPyP is known to catalyze the dismutation of O-2.(-), and using stopped-flow spectrophotometry, the rate of Mn(III)TMPyP-catalyzed dismutation has been measured directly (k(c)= 1.1 x 10(7) M-1 s(-1)). Further, O-2.(-), like the biological antioxidants, rapidly reduces oxoMn(IV) to the Mn(III) oxidation state (k approximate to 10(8) M-1 s(-1)), transforming Mn(III)TMPyP into a O-2.(-)-coupled ONOO- reductase. Under conditions of oxidative stress and reduced antioxidant levels, Mn(III)TMPyP may deplete O-2.(-) primarily as a function of its ONOO- reductase activity, and not through its O-2.(-) dismutase activity.

  DOI：

  10.1021/ja9801036

文献信息

• Electrocatalytic reduction of dioxygen by Mn(<scp>iii</scp>) <i>meso</i>-tetra(<i>N</i>-methylpyridinium-4-yl)porphyrin in universal buffer
  作者：Lauren E. Lieske、Shelby L. Hooe、Asa W. Nichols、Charles W. Machan

  DOI：10.1039/c9dt01436e

  日期：——

  characterization of manganese(III) meso-tetra(N-methylpyridinium-4-yl)porphyrin pentachloride ([Mn(TMPyP)Cl][Cl]4) via cyclic voltammetry (CV) and UV-vis spectroelectrochemistry (UV-vis SEC) was performed across the entire pH domain in aqueous buffered conditions. Assessment of the homogeneous electrocatalytic efficiency for the oxygen reduction reaction (ORR) from pH 3 to 6 using rotating-ring disk electrode experiments

  锰（III）介孔四（N-甲基吡啶-4-基）卟啉五氯化物（[Mn（TMPyP）Cl] [Cl] 4）的电化学表征通过循环伏安法（CV）和紫外可见光谱电化学（UV-vis SEC）在水缓冲条件下在整个pH域内进行。使用旋转环盘电极实验（RRDE）对pH值为3至6的氧还原反应（ORR）的均相电催化效率进行评估，发现它对水具有选择性（82％至93％）。观察到的水效率与先前有关锰卟啉在水系统中电催化ORR活性的报道相反，后者鉴定出H 2 O 2。作为仅使用间接RDE方法的主要产品。此处描述的结果与关于锰卟啉在非水条件下的电催化行为的最新报道相一致，其中通过RRDE方法也确定了对水的相似选择性。在pH值为1时，UV-vis SEC实验还表明发生了分解。施加还原电位后观察到游离碱卟啉。
• Detection and Characterization of an Oxomanganese(V) Porphyrin Complex by Rapid-Mixing Stopped-Flow Spectrophotometry
  作者：John T. Groves、Jinbo Lee、Sudhakar S. Marla

  DOI：10.1021/ja962605u

  日期：1997.7.1

  The Soret maximum of 1 was found at 443 nm, intermediate between that of oxomanganese(IV) (428 nm) and Mn(III)TMPyP (462 nm), thus facilitating its detection. The rate of formation of 1 from Mn(III)TMPyP followed second-order kinetics, first order in Mn(III) porphyrin and first order in oxidant. The rate constants have the following order: m-CPBA (2.7 × 107 M-1 s-1) > HSO5- (6.9 × 105 M-1 s-1) ≈ ClO-

  描述了在环境催化条件下首次检测和表征氧锰 (V) 卟啉配合物。(四-(N-甲基吡啶基)卟啉基)锰(III) [Mn(III)TMPyP] 与多种氧化剂如间氯过氧苯甲酸 (m-CPBA)、HSO5- 和 ClO- 的反应已显示通过停流分光光度法生产相同的、短寿命的中间体 (1)。在 443 nm 处发现 Soret 最大值为 1，介于氧锰 (IV) (428 nm) 和 Mn (III) TMPyP (462 nm) 之间，从而促进其检测。从 Mn(III)TMPyP 形成 1 的速率遵循二级动力学，在 Mn(III) 卟啉中为一级，在氧化剂中为一级。速率常数具有以下顺序：m-CPBA (2.7 × 107 M-1 s-1) > HSO5- (6.9 × 105 M-1 s-1) ≈ ClO- (6.3 × 105 M-1 s-1) . 一旦形成，中间物种 1 通过单电子还原快速转化为 oxoMn(IV)
• Water Exchange on Manganese(III) Porphyrins. Mechanistic Insights Relevant for Oxygen Evolving Complex and Superoxide Dismutation Catalysis
  作者：Dominik Lieb、Achim Zahl、Tatyana E. Shubina、Ivana Ivanović-Burmazović

  DOI：10.1021/ja1014585

  日期：2010.6.2

  (DeltaH(double dagger), DeltaS(double dagger), and DeltaV(double dagger)) for the water exchange process on Mn(III) centers have experimentally been determined using temperature and pressure dependent (17)O NMR techniques. For the investigations the Mn(III) porphyrin complexes [Mn(III)(TPPS)S(2)](n-) and [Mn(III)(TMpyP)S(2)](n+) (S = H(2)O and/or OH(-)) have been selected due to their high solution stability in

  在这项工作中，Mn(III) 中心的水交换过程的速率常数 (k(ex)) 和激活参数 (DeltaH(double dagger)、DeltaS(double dagger) 和 DeltaV(double dagger)) 已经通过实验得到使用温度和压力相关的 (17)O NMR 技术确定。为了研究 Mn(III) 卟啉复合物 [Mn(III)(TPPS)S(2)](n-) 和 [Mn(III)(TMpyP)S(2)](n+) (S = H(2) )O 和/​​或 OH(-)) 之所以被选中，是因为它们在很宽的 pH 值范围内具有高溶液稳定性，从而能够在 diaqua 和 aqua-hydroxo 复合物的情况下测量水交换。我们已经通过实验证明，Mn(III) 卟啉的水交换是 I(d) 到 I 机制的快速过程 (k(ex) 大约 = 10(7) s(-1))，受 Jahn-Teller