[RuCl₃(4′MeO-trpy)] | 1012796-62-1

• 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: [RuCl₃(4′MeO-trpy)]
• 英文别名: [ruthenium(III)(chloride)₃(4′-methoxy-2,2′:6′,2″-terpyridine)]；RuCl3(4'-methoxy-2,2':6',2''-terpyridine)；Ru(4'-methoxy-2,2':6',2''-terpyridine)Cl3；4-methoxy-2,6-dipyridin-2-ylpyridine;trichlororuthenium
• CAS: 1012796-62-1
• 化学式: C₁₆H₁₃Cl₃N₃ORu
• 分子量: 470.728
• InChiKey: KJKJMEYBCKHPIF-UHFFFAOYSA-K

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：

  [RuCl₃(4′MeO-trpy)] 在 N-ethylmorpholine 作用下， 以 甲醇 、 水 、 重水 为溶剂， 生成 [Ru(II)(4'-methoxy-2,2':6',2''-terpyridine)(4,4'-dimethoxy-2,2'-bipyridine)(D2O)](2+)
  参考文献：
  名称：

  Insight into Water Oxidation by Mononuclear Polypyridyl Ru Catalysts

  摘要：

  A family of compounds based on the mononuclear coordination complex [Ru(tpy)(bpy)(OH2)](2+) (1b; tpy=2,2':6',2 ''-terpyridine, bpy=2,2'-bipyridine) are shown to be competent catalysts in the Ce(IV)-driven oxidation of water in acidic media. The systematic installation of electron-withdrawing (e.g., -Cl, -COOH) and -donating (e.g., -OMe) groups at various positions about the periphery of the polypyridyl framework offers insight into how electronic parameters affect the properties of water oxidation catalysts, It is observed, in general, that electron-withdrawing groups (EWGs) on the bpy ligands suppress catalytic activity (k(obs)) and enhance catalytic turnover numbers (TONs); conversely, the presence of electron-donating groups (EDGs) accelerate catalytic rates while decreasing catalyst stability. We found that 2,2'-bipyridine N,N'-dioxide is produced when 1b is subject to excess Ce(IV) in acidic media, which suggests that dissociation of the bpy ligand is a source of catalyst deactivation and/or decomposition. Density functional theory (DFT) calculations corroborate these findings by showing that the Ru-N-bpy bond trans to the O atom is weakened at higher oxidation levels while the other Ru-N bonds are affected to a lesser extent. We also show that the Ru-Cl bond is not robust in aqueous media, which has implications in studying the catalytic behavior of systems of this type.

  DOI：

  10.1021/ic902024s
• 作为产物：
  描述：

  ruthenium(III) chloride trihydrate 、 4'-甲氧基-2,2':6',2''-三联吡啶 以 乙醇 为溶剂， 反应 4.0h， 以92%的产率得到[RuCl₃(4′MeO-trpy)]
  参考文献：
  名称：

  全氟烷基C8H17标签轴承链修饰的单核Ru（II）聚吡啶基水氧化催化剂

  摘要：

  合成了一套新颖的，带有一个，两个或三个C 8 F 17标签的聚吡啶基Ru（II）配合物1-7，并通过NMR，UV / Vis光谱法进行了表征，在一系列配合物1-3的情况下，5和7通过X射线衍射在单晶上进行。的固态结构3，5和7也进行计算DFT的研究，以便深入了解不同数目的全氟化标签的它们在固态稳定性的影响。络合物在强氧化条件下在溶液中稳定，并确实以其水合形式保持催化活性（1'-7'）与母体复合物8'很好地比较，并且它们的两亲性质可以使其掺入荧光介质和界面中。

  DOI：

  10.1002/ejic.201900579

文献信息

• Critical Hammett Electron-Donating Ability of Substituent Groups for Efficient Water Oxidation Catalysis by Mononuclear Ruthenium Aquo Complexes
  作者：Shunsuke Watabe、Yuki Tanahashi、Masanari Hirahara、Hirosato Yamazaki、Kosuke Takahashi、Eman A. Mohamed、Yuta Tsubonouchi、Zaki N. Zahran、Kenji Saito、Tatsuto Yui、Masayuki Yagi

  DOI：10.1021/acs.inorgchem.9b01623

  日期：2019.10.7

  [Ru(Rtpy)(bpy)(H2O)]2+ (1R; bpy = 2,2′-bipyridine, and Rtpy = 2,2′:6′,2″-terpyridine derivatives) complexes with a variety of 4′-substituent groups on Rtpy were synthesized and characterized to reveal the effects of substituents on their structures, physicochemical properties, and catalytic activities for water oxidation. The geometric structures of 1R are not considerably influenced by the electron-donating

  [Ru（Rtpy）（bpy）（H 2 O）] 2+（1R ; bpy = 2,2'-联吡啶，Rtpy = 2,2'：6'，2''-叔吡啶衍生物）配合物合成并表征了Rtpy上的4'-取代基，以揭示取代基对其结构，理化性质和对水氧化的催化活性的影响。1R的几何结构不受Rtpy上4'取代基的供电子能力影响。对于1R观察到类似的多步质子偶联电子转移反应并且，随着取代基的供电子能力的增加，每个氧化步骤的氧化还原电势趋于降低，这可以解释为供电子基团在Ru中心的电子密度增加，从而稳定了积聚的正电荷。在氧化时。这与由于Ru中心的d轨道能级增加而分配给1R的金属到配体电荷转移跃迁的480 nm附近吸收带的红移一致。然而，水氧化催化反应的1R转换频率（k O 2）很大程度上取决于Rtpy配体，范围从0.05×10 –2到44×10 –2 s –1（因为观察到R =乙氧基的最高k O 2）是880倍。4'-取代
• Water oxidation catalysis with ligand substituted Ru–bpp type complexes
  作者：Stephan Roeser、Fernando Bozoglian、Craig J. Richmond、Aaron B. League、Mehmed Z. Ertem、Laia Francàs、Pere Miró、Jordi Benet-Buchholz、Christopher J. Cramer、Antoni Llobet

  DOI：10.1039/c6cy00197a

  日期：——

  also been solved. Kinetic analysis monitored by UV-vis spectroscopy reveals the electronic effects exerted by the ED and EW groups on the substitution kinetics and stoichiometric water oxidation reaction. The catalytic water oxidation activity is evaluated by means of chemically (CeIV), electrochemically, and photochemically induced processes. It is found that, in general, ED groups do not strongly affect

  一系列通式的对称和非对称的双核钌络合物[茹（R 2 -trpy）（H 2 O）]的[Ru（R 3 -trpy）（H 2 O）]（μ-R 1个-BPP ）} 3+其中trpy是2,2'：6'，2'' -三联吡啶，BPP -是3,5-双（2-吡啶基）-pyrazolate和R 1，R 2和R 3为供电子（ED ）和吸电子（EW）基团，例如Me，MeO，NH 2和NO 2已经使用微波辅助技术制备。这些配合物已通过分析（元素分析），光谱（UV-vis，NMR）和电化学（CV，SQWV，CPE）技术进行了全面表征。还解决了一种乙酸盐和一种氯桥联前体的单晶X射线结构。通过紫外-可见光谱监测的动力学分析揭示了ED和EW基团对取代动力学和化学计量的水氧化反应产生的电子效应。催化水的氧化活性通过化学方法（Ce IV），电化学和光化学诱导的过程。已经发现，通常，ED基团不会强烈影响催化速率，而EW基团则大大
• Micromodulating the Electronic Coupling Across Redox-Active Ferrocenyl Spacer in Binuclear Ruthenium(II) Terpyridine Complexes: Synthesis, Electrochemistry, and Photophysical Properties
  作者：Teng-Yuan Dong、Hung-Yu Lin、Shu-Fan Lin、Chia-Chen Huang、Yuh-Sheng Wen、Liangshiu Lee

  DOI：10.1021/om700568h

  日期：2008.2.1

  electrochemical and photophysical properties of [(X-tpy)RuII(tpy-(fc)2-tpy)RuII(X-tpy)]4+ (tpy = terpyridyl; X = −H (1a), −OCH3 (1b), −Cl (1c); fc = ferrocenyl) and [(X-tpy)RuII(tpy-C≡C-(fc)2-C≡C-tpy)RuII(X-tpy)]4+ (X = −H (2a), −OCH3 (2b), −Cl (2c)) are described. The ground-state HOMO and LUMO energies were probed by electrochemical measurements. The excited-state photophysical properties were probed by

  [[X- tpy ）Ru II（tpy-（fc）2 -tpy）Ru II（X- tpy ）] 4+的电化学和光物理性质（tpy =吡啶基; X = -H（1a），-OCH 3（1b），-Cl（1c）; fc =二茂铁基）和[[X-tpy）Ru II（tpy-C≡C-（fc）2 -C≡C-tpy）Ru II（X-tpy）] 4 +（X = -H（2a），-OCH 3（2b），-Cl（2c））进行了说明。通过电化学测量探测基态HOMO和LUMO能量。紫外可见吸收光谱和发光光谱探测了激发态的光物理性质。的复合物1A - Ç是非发射（λ EXC在脱氧的纯CH 480-580纳米）3 CN或H 2 O / CH 3 CN（4/1）溶液在25℃下。络合物2a - c在H 2 O / CH 3 CN（4/1）溶液中具有室温发光。比较2b，c和2a的发光特性，-OCH 3和-Cl取代基的附着导致发光量子产率的降低和三重态寿命的降低。