Ru(bda)(isoq)₂

• 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: Ru(bda)(isoq)₂
• 英文别名: Ru(2,2'-bipyridine-6,6'-dicarboxylate)(isoquinoline)₂；6-(6-carboxylatopyridin-2-yl)pyridine-2-carboxylate;isoquinoline;ruthenium(2+)
• 化学式: C₃₀H₂₀N₄O₄Ru
• 分子量: 601.583
• InChiKey: GGKTXUNPANMLIX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.34
• 重原子数：
  39
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  132
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Ru(bda)(isoq)₂ 、 乙腈 在 sodium perchlorate 作用下， 生成
  参考文献：
  名称：

  Electron Transfer Mediator Effects in the Oxidative Activation of a Ruthenium Dicarboxylate Water Oxidation Catalyst

  摘要：

  The mechanism of electrocatalytic water oxidation by the water oxidation catalyst, ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) bis-isoquinoline (isoq), [Ru(bda)(isoq)(2)], 1, at metal oxide electrodes has been investigated. At indium-doped tin oxide (ITO), diminished catalytic currents and increased overpotentials are observed compared to glassy carbon (GC). At pH 7.2 in 0.5 M NaClO4, catalytic activity is enhanced by the addition of [Ru(bpy)3](2+) (bpy = bipyridine) as a redox mediator. Enhanced catalytic rates are also observed at ITO electrodes derivatized with the surface-bound phosphonic acid derivative [Ru(4,4'-(PO3H2)(2)bpy)(bpy)(2)](2+), RuP2+. Controlled potential electrolysis with measurement of O-2 at ITO with and without surface-bound RuP2+ confirm that water oxidation catalysis occurs. Remarkable rate enhancements are observed with added acetate and phosphate, consistent with an important mechanistic role for atom-proton transfer (APT) in the rate-limiting step as described previously at GC electrodes.

  DOI：

  10.1021/acscatal.5b00720
• 作为产物：
  描述：

  异喹啉 、 dichlorotetrakis(dimethylsulfoxide)ruthenium(II) 、 2,2'-联吡啶-6,6'-二羧酸 在 三乙胺 作用下， 以 甲醇 为溶剂， 以45 %的产率得到Ru(bda)(isoq)₂
  参考文献：
  名称：

  脂质双层-水界面光催化水氧化电荷转移动力学的机理洞察

  摘要：

  光系统 II 是天然的水氧化系统，是嵌入磷脂膜中的大型蛋白质复合物。一个更简单的光催化水氧化系统由用两亲性钌 (II)-三-联吡啶光敏剂 (PS) 和 6,6'-dicarboxylato-2,2'-联吡啶-钌 (II) 催化剂 (Cat) 功能化的脂质体组成水溶性牺牲电子受体（Na 2 S 2 O 8). 然而，将这种光催化系统嵌入脂质体膜对光催化水氧化机制的影响尚不清楚。在这里，光谱工具已经确定了几种现象，这些现象解释了与类似的均相系统相比，水光氧化脂质体的动力学截然不同。首先，S 2 O 8 2–在脂质体表面对光激发的 PS* 的氧化猝灭仅通过静态猝灭发生，而在均相系统中观察到动态猝灭。此外，淬灭反应后的电荷分离效率远小于单位，与 PS +的定量生成相反在均匀溶液中。同时，膜结合 PS 的局部高浓度会在 10:1–40:1 的脂质-PS 摩尔比下引起自淬灭。最后，虽然从 PS +到催化剂的空穴转移在均相溶液中相当快（k

  DOI：

  10.1021/jacs.2c06842
• 作为试剂：
  描述：

  2,6-二甲基吡啶 、 三氟甲磺酸钠 在 sodium persulfate 、 tris(2,2'-bipyridyl)ruthenium(II) trifluoromethanesulfonate 、 Ru(bda)(isoq)₂ 、 水 、 calcium chloride 作用下， 以 乙腈 为溶剂， 以485 mg的产率得到2,6-lutidinium triflate
  参考文献：
  名称：

  水质子源在环境反应条件下将二氮催化转化为氨

  摘要：

  最佳模型：在环境反应条件下，钼的催化将分子中的二氮转化为氨，这是通过使用钌的水氧化原位生成的质子源与可见光和光敏剂相结合而实现的。本反应体系被认为是光合细菌固氮的新模型。

  DOI：

  10.1002/asia.201701067

文献信息

• Highly efficient and robust molecular water oxidation catalysts based on ruthenium complexes
  作者：Lei Wang、Lele Duan、Ying Wang、Mårten S. G. Ahlquist、Licheng Sun

  DOI：10.1039/c4cc05069j

  日期：——

  The molecular catalyst Ru(bda)L₂ (H₂bda = 2,2′-bipyridine-6,6′-dicarboxylic acid, L = 6-bromophthalazine) shows excellent catalytic activity for water oxidation. By using Ce(NH₄)₂(NO₃)₆ as an oxidant, the catalyst reached a high turnover number TON = 100 000 in 3 hours.

  Ru(bda)L₂（H₂bda = 2,2′-联吡啶-6,6′-二羧酸，L = 6-溴酞噻嗪）分子催化剂显示出优异的水氧化催化活性。通过使用Ce(NH₄)₂(NO₃)₆作为氧化剂，该催化剂在3小时内达到了高的周转数TON = 100,000。
• Ruthenium-catalysed oxidative conversion of ammonia into dinitrogen
  作者：Kazunari Nakajima、Hiroki Toda、Ken Sakata、Yoshiaki Nishibayashi

  DOI：10.1038/s41557-019-0293-y

  日期：2019.8

  Conversion of ammonia into dinitrogen has attracted broad scientific interest in relation to molecular models of the heterogeneous nitrogen fixation process, environmental treatment for denitrification and utilization of ammonia as an energy carrier. Here we show that some ruthenium complexes bearing 2,2'-bipyridyl-6,6'-dicarboxylate ligands work as catalysts for the ammonia oxidation reaction. Production

  关于异质固氮过程的分子模型，反硝化的环境处理以及氨作为能量载体的利用，氨向二氮的转化已经引起了广泛的科学兴趣。在这里，我们表明一些带有2,2'-联吡啶基-6,6'-二羧酸酯配体的钌配合物可作为氨氧化反应的催化剂。当在钌催化剂存在下用三芳基ami基自由基作为氧化剂和2,4,6-可力丁作为碱处理铵盐时，观察到产生二氮。基于某些中间体的表征，我们提出了一种通过双金属氮化物-氮化物偶联过程的反应途径。所提出的反应途径得到密度泛函理论计算的支持。
• Electron Transfer Mediator Effects in the Oxidative Activation of a Ruthenium Dicarboxylate Water Oxidation Catalyst
  作者：Matthew V. Sheridan、Benjamin D. Sherman、Zhen Fang、Kyung-Ryang Wee、Michael K. Coggins、Thomas J. Meyer

  DOI：10.1021/acscatal.5b00720

  日期：2015.7.2

  The mechanism of electrocatalytic water oxidation by the water oxidation catalyst, ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) bis-isoquinoline (isoq), [Ru(bda)(isoq)(2)], 1, at metal oxide electrodes has been investigated. At indium-doped tin oxide (ITO), diminished catalytic currents and increased overpotentials are observed compared to glassy carbon (GC). At pH 7.2 in 0.5 M NaClO4, catalytic activity is enhanced by the addition of [Ru(bpy)3](2+) (bpy = bipyridine) as a redox mediator. Enhanced catalytic rates are also observed at ITO electrodes derivatized with the surface-bound phosphonic acid derivative [Ru(4,4'-(PO3H2)(2)bpy)(bpy)(2)](2+), RuP2+. Controlled potential electrolysis with measurement of O-2 at ITO with and without surface-bound RuP2+ confirm that water oxidation catalysis occurs. Remarkable rate enhancements are observed with added acetate and phosphate, consistent with an important mechanistic role for atom-proton transfer (APT) in the rate-limiting step as described previously at GC electrodes.
• Mechanistic Insights into the Charge Transfer Dynamics of Photocatalytic Water Oxidation at the Lipid Bilayer–Water Interface
  作者：Hongwei Song、Agnese Amati、Andrea Pannwitz、Sylvestre Bonnet、Leif Hammarström

  DOI：10.1021/jacs.2c06842

  日期：2022.10.26

  transfer from PS+ to catalyst is rather fast in homogeneous solution (kobs > 1 × 104 s–1 at [catalyst] > 50 μM), in liposomes at pH = 4, the reaction is rather slow (kobs ≈ 17 s–1 for 5 μM catalyst in 100 μM DMPC lipid). Overall, the better understanding of these productive and unproductive pathways explains what limits the rate of photocatalytic water oxidation in liposomal vs homogeneous systems, which

  光系统 II 是天然的水氧化系统，是嵌入磷脂膜中的大型蛋白质复合物。一个更简单的光催化水氧化系统由用两亲性钌 (II)-三-联吡啶光敏剂 (PS) 和 6,6'-dicarboxylato-2,2'-联吡啶-钌 (II) 催化剂 (Cat) 功能化的脂质体组成水溶性牺牲电子受体（Na 2 S 2 O 8). 然而，将这种光催化系统嵌入脂质体膜对光催化水氧化机制的影响尚不清楚。在这里，光谱工具已经确定了几种现象，这些现象解释了与类似的均相系统相比，水光氧化脂质体的动力学截然不同。首先，S 2 O 8 2–在脂质体表面对光激发的 PS* 的氧化猝灭仅通过静态猝灭发生，而在均相系统中观察到动态猝灭。此外，淬灭反应后的电荷分离效率远小于单位，与 PS +的定量生成相反在均匀溶液中。同时，膜结合 PS 的局部高浓度会在 10:1–40:1 的脂质-PS 摩尔比下引起自淬灭。最后，虽然从 PS +到催化剂的空穴转移在均相溶液中相当快（k