[Rh(4,4’-dimethyl-2,2’-bipyridine)2Cl2]Cl | 75766-96-0

• 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: [Rh(4,4’-dimethyl-2,2’-bipyridine)2Cl2]Cl
• 英文别名: {Rh(4,4'-dimethyl-2,2'-bipyridine)2Cl2}Cl；[Rh(III)(4,4'-dimethyl-2,2'-bipyridine)2Cl2]Cl
• CAS: 75766-96-0
• 化学式: C₂₄H₂₄Cl₂N₄Rh*Cl
• 分子量: 577.746
• InChiKey: ZSMGBKFHLVSFCR-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [Rh(4,4’-dimethyl-2,2’-bipyridine)2Cl2]Cl 、 1,2-双(4'-甲基-2,2'-联吡啶-4-基)乙烷 在 高氯酸 作用下， 以 乙醇 、 乙二醇 为溶剂， 生成 {Rh(4,4'-dimethyl-2,2'-bipyridine)2{1,2-bis(4-(4'-methyl-2,2'-bipyridyl))ethane}}(ClO3)3*H2O
  参考文献：
  名称：

  Four Intercomponent Processes in a Ru(II)-Rh(III) Polypyridine Dyad: Electron Transfer from Excited Donor, Electron Transfer to Excited Acceptor, Charge Recombination, and Electronic Energy Transfer

  摘要：

  The binuclear complex Ru-II(Me(2)phen)(2)-(Mebpy-CH2-CH2-Mebpy)-Rh-III(Me(2)pby)(2)(5+) (Me(2)phen = 4,7-dimethyl-1,10- phenanthroline; Mebpy = 4-methyl-2,2'-bipyridine; Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine), hereafter represented by Ru(II)-Rh(III), was synthesized and studied. Selective excitation of the two moieties of the dyad was achieved with visible (100% *Ru(II)-Rh(III)) or ultraviolet light (e.g., at 298 nm, 70% Ru(II)-*Rh(III)), In room-temperature fluid solutions, both local excited states are quenched by electron transfer, leading to a common Ru(III)-Rh(II) state. The two forward electron-transfer processes, as well as the recombination process leading back to the ground state, can be resolved by transient laser spectroscopy, using various excitation wavelengths and pulse widths (532 nm, 30 ps; 427 nm, 0.5 ps; 298 nm, 0.5 ps). Rate constants in acetonitrile are as follows: *Ru(II)-Rh(III) --> Ru(III)-Rh(II), 1.7 X 10(8) s(-1); Ru(II)-*Rh(III) --> Ru(III)-Rh(II), 3.3 x 10(10) s(-1); Ru(III)-Rh(II) --> Ru(II)-Rh(III), 7.1 x 10(9) s(-1). The rate constants can be rationalized in terms of standard electron-transfer theory, assuming that the driving force (Delta G degrees =-0.10, -0.70, and -2.07 eV, respectively) is the main variable parameter. The two forward processes belong to the ''normal'', and the back reaction belongs to the ''inverted'' free-energy regime. In room-temperature fluid solution, no Ru(II)-*Rh(III) --> *Ru(II)-Rh(III) energy transfer (Delta G degrees =-0.61 eV) is observed, presumably because of efficient competition by the faster Ru(II)-*Rh(III) --> Ru(III)-Rh(II) electron-transfer quenching. By contrast, this process becomes efficient in rigid media (room-temperature or 77 K), where both the *Ru(II)-Rh(III) --> Ru(III)-Rh(II) and Ru(II)-*Rh(III) --> Ru(III)-Rh(II) electron-transfer processes are blocked as a consequence of restricted solvent repolarization. In 77 K ethanol glass, the energy-transfer rate constant is 1.9 X 10(6) s(-1).

  DOI：

  10.1021/ja00088a013
• 作为试剂：
  描述：

  水 在 顺-双(2,2'-二吡啶基)二氯化钌(II)二水合物 、 [Rh(4,4’-dimethyl-2,2’-bipyridine)2Cl2]Cl 、 Vitamin C 、 sodium ascorbate 作用下， 生成 氢气
  参考文献：
  名称：

  [RhIII（dmbpy）2Cl2] +作为在纯水中可见光驱动制氢的高效催化剂：与其他铑催化剂的比较

  摘要：

  我们报告了一个非常有效的均相系统，用于在室温下在纯水溶液中以可见光驱动制氢。这包括作为催化剂的[Rh III（dmbpy）2 Cl 2 ] Cl（1），作为光敏剂的[Ru（bpy）3 ] Cl 2（PS1）和作为牺牲电子给体的抗坏血酸。还使用其他已知的铑催化剂或铱光敏剂在水溶液中进行了比较研究，结果表明1）PS1 / 1与以前报道的铑催化剂Na 3 [Rh I（dpm）3 Cl]和[Rh III ]相比，/抗坏血酸/抗坏血酸系统是迄今为止最活跃的基于铑的均相光催化体系，用于在纯水介质中制氢。（bpy）Cp *（H 2 O）] SO 4和2）当将[Ir III（ppy）2（bpy）] Cl（PS2）用作光敏剂时，系统效率较低。由于催化剂1是水中最有效的铑基H 2演化催化剂，因此通过改变PS1 /可以进一步研究该配合物的性能极限。在pH 4.0下为1的比例 在最佳条件下，与催化剂相比，该系统最

  DOI：

  10.1002/chem.201202555

文献信息

• Photoinduced Electron Transfer across Oligo-<i>p</i>-phenylene Bridges. Distance and Conformational Effects in Ru(II)−Rh(III) Dyads
  作者：Maria Teresa Indelli、Claudio Chiorboli、Lucia Flamigni、Luisa De Cola、Franco Scandola

  DOI：10.1021/ic700430u

  日期：2007.7.1

  series of rodlike ruthenium(II)-rhodium(III) polypyridine dyads based on modular oligo-p-phenylene bridges, of the general formula [(Me2phen)2Ru-bpy-(ph)n-bpy-Rh(Me2bpy)]5+ (Me2phen=4,7-dimethyl-1,10-phenanthroline; bpy=2,2'-bipyridine; ph=1,4-phenylene; n=1-3), have been synthesized and their photophysical properties investigated. The dyad [(Me2bpy)2Ru-bpy-(ph)3'-bpy-Rh(Me2bpy)]5+ with the central

  基于通式[（Me2phen）2Ru-bpy-（ph）n-bpy-Rh（Me2bpy）] 5的一系列基于模块化低聚对亚苯基桥的棒状钌（II）-铑（III）聚吡啶二联体+（Me2phen = 4,7-二甲基-1,10-菲咯啉; bpy = 2,2'-联吡啶; ph = 1,4-亚苯基; n = 1-3），并对其光物理性质进行了研究。还研究了带有中心亚苯基带有两个己基链的二元[（Me2bpy）2Ru-bpy-（ph）3'-bpy-Rh（Me2bpy）] 5+。对于该系列中最长（n = 3）的垫片，金属到金属的距离达到24A。对于室温CH3CN溶液中的所有二元组，观察到Ru基发色单元的典型金属到配体电荷转移发光的猝灭，这表明发生了从激发的Ru部分到Rh基单元的分子内光诱导电子的有效转移。通过纳秒和皮秒级的时间分辨发射和吸收光谱法确定了电子转移过程的速率常数。观察到实验传输速率对桥长度的指数依赖性，