[NMe4][Mn(II)(N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido)] | 1311309-91-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [NMe4][Mn(II)(N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido)]
• CAS: 1311309-91-7
• 化学式: C₄H₁₂N*C₃₃H₄₅MnN₄O₆S₃
• 分子量: 819.025
• InChiKey: TUKLVIMJNOVYDZ-UHFFFAOYSA-N

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：

  15-冠醚-5 、 [NMe4][Mn(II)(N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido)] 、 calcium(II) trifluoromethanesulfonate 在 O₂ 作用下， 以 二氯甲烷 为溶剂， 以50%的产率得到[15-crown-5.cntns.Ca(II)-(μ-OH)-Mn(III)(N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido))](1+)
  参考文献：
  名称：

  The Effects of Redox-Inactive Metal Ions on the Activation of Dioxygen: Isolation and Characterization of a Heterobimetallic Complex Containing a Mn^III–(μ-OH)–Ca^II Core

  摘要：

  Rate enhancements for the reduction of dioxygen by a Mn-II complex were observed in the presence of redox-inactive group 2 metal ions. The rate changes were correlated with an increase in the Lewis acidity of the group 2 metal ions. These studies led to the isolation of heterobimetallic complexes containing Mn-III-(mu-OH)-M-II cores (M-II = Ca-II, Ba-II) in which the hydroxo oxygen atom is derived from O-2. This type of core structure has relevance to the oxygen-evolving complex within photosystem II.

  DOI：

  10.1021/ja203458d
• 作为产物：
  描述：

  N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamide) 、 四甲基醋酸铵 、 manganese(II) acetate 在 NaH 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 以90%的产率得到[NMe4][Mn(II)(N,N',N''-[2,2',2''-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido)]
  参考文献：
  名称：

  The Effects of Redox-Inactive Metal Ions on the Activation of Dioxygen: Isolation and Characterization of a Heterobimetallic Complex Containing a Mn^III–(μ-OH)–Ca^II Core

  摘要：

  Rate enhancements for the reduction of dioxygen by a Mn-II complex were observed in the presence of redox-inactive group 2 metal ions. The rate changes were correlated with an increase in the Lewis acidity of the group 2 metal ions. These studies led to the isolation of heterobimetallic complexes containing Mn-III-(mu-OH)-M-II cores (M-II = Ca-II, Ba-II) in which the hydroxo oxygen atom is derived from O-2. This type of core structure has relevance to the oxygen-evolving complex within photosystem II.

  DOI：

  10.1021/ja203458d

文献信息

• Heterobimetallic complexes with M^III-(μ-OH)-M^IIcores (M^III= Fe, Mn, Ga; M^II= Ca, Sr, and Ba): structural, kinetic, and redox properties
  作者：Young Jun Park、Sarah A. Cook、Nathaniel S. Sickerman、Yohei Sano、Joseph W. Ziller、A. S. Borovik

  DOI：10.1039/c2sc21400h

  日期：——

  The effects of redox-inactive metal ions on dioxygen activation were explored using a new FeII complex containing a tripodal ligand with 3 sulfonamido groups. This iron complex exhibited a faster initial rate for the reduction of O2 than its MnII analog. Increases in initial rates were also observed in the presence of group 2 metal ions for both the FeII and MnII complexes, which followed the trend NMe4+ < BaII < CaII = SrII. These studies led to the isolation of heterobimetallic complexes containing FeIII-(μ-OH)-MII cores (MII = Ca, Sr, and Ba) and one with a [SrII(OH)MnIII]+ motif. The analogous [CaII(OH)GaIII]+ complex was also prepared and its solid state molecular structure is nearly identical to that of the [CaII(OH)FeIII]+ system. Nuclear magnetic resonance studies indicated that the diamagnetic [CaII(OH)GaIII]+ complex retained its structure in solution. Electrochemical measurements on the heterobimetallic systems revealed similar one-electron reduction potentials for the [CaII(OH)FeIII]+ and [SrII(OH)FeIII]+ complexes, which were more positive than the potential observed for [BaII(OH)FeIII]+. Similar results were obtained for the heterobimetallic MnII complexes. These findings suggest that Lewis acidity is not the only factor to consider when evaluating the effects of group 2 ions on redox processes, including those within the oxygen-evolving complex of Photosystem II.

  研究人员使用了一种新的含有 3 个磺酰胺基团的三足配体的 FeII 复合物，探讨了氧化还原不活跃的金属离子对二氧活化的影响。与 MnII 类似物相比，这种铁络合物的 O2 还原初始速率更快。在有第 2 族金属离子存在的情况下，FeII 和 MnII 复合物的初始速率也会增加，其趋势为 NMe4+ < BaII < CaII = SrII。通过这些研究，我们分离出了含有 FeIII-(δ-OH)-MII 核心（MII = Ca、Sr 和 Ba）的杂双金属配合物，以及一种具有 [SrII(OH)MnIII]+ 主题的配合物。此外，还制备了类似的 [CaII(OH)GaIII]+ 复合物，其固态分子结构与 [CaII(OH)FeIII]+ 系统几乎相同。核磁共振研究表明，二磁性 [CaII(OH)GaIII]+ 复合物在溶液中保持其结构。对杂双金属体系进行的电化学测量显示，[CaII(OH)FeIII]+ 和 [SrII(OH)FeIII]+ 复合物具有相似的单电子还原电位，比[BaII(OH)FeIII]+ 的电位更正。杂多金属 MnII 复合物也得到了类似的结果。这些研究结果表明，在评估第 2 组离子对氧化还原过程（包括光系统 II 氧发生复合物中的氧化还原过程）的影响时，路易斯酸性并不是唯一需要考虑的因素。