[(2,2'-bipyridine)2(H2O)Ru(III)ORu(III)(OH2)(2,2'-bipyridine)](4+) | 96364-19-1

• 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: [(2,2'-bipyridine)2(H2O)Ru(III)ORu(III)(OH2)(2,2'-bipyridine)](4+)
• 英文别名: {(2,2'-bipyridine)2(OH2)Ru}2O(4+)；μ-oxo bis[aquabis(2,2'-bipyridine) ruthenium(III)]；[Ru(2,2'-bipyridine)2(water)]2O(4+)；cis,cis-[(2,2'bipyridine)2(H2O)Ru(III)ORu(III)(H2O)(2,2'-bipyridine)2](4+)；cis,cis-[(2,2'-bipyridine)2(H2O)Ru(III)ORu(III)(OH2)(2,2'-bipyridine)2](4+)
• CAS: 96364-19-1
• 化学式: C₄₀H₃₆N₈O₃Ru₂
• 分子量: 878.918
• InChiKey: VYIONOUPNJIJDV-UHFFFAOYSA-N

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：

  [(2,2'-bipyridine)2(H2O)Ru(III)ORu(III)(OH2)(2,2'-bipyridine)](4+) 在 magnesium 、 calf thymus DNA 作用下， 以 水 为溶剂， 生成 [(2,2'-bipyridine)2Ru(H2O)2](2+)
  参考文献：
  名称：

  [[bpy）2（OH2）RuIIIORuIII（H2O）（bpy）2] 4+裂解Mg2 +激活的双链DNA

  摘要：

  已经研究了标题复合物与DNA的反应。如吸收光谱法和循环伏安法所示，向DNA中添加[（bpy）2（OH2）RuORu（OH2）（bpy）2] 4+导致该络合物还原为Ru（bpy）2（OH2）22+。 。Mg2 +促进了反应。结合的证据指出了一种机理，其中羰基桥连接的二聚体被水解成单体Ru（III）络合物，该络合物能够氧化DNA以实现链断裂。凝胶电泳显示[（bpy）2（OH2）RuORu（OH2）（bpy）2] 4+对超螺旋/ gfX174 DNA形成切口，并且在存在Mg2 +的情况下观察到双链裂解。在用复合物处理之前，质粒的线性化不会导致进一步的片段化，这表明需要超螺旋才能实现双链裂解。

  DOI：

  10.1016/0020-1693(95)04550-3
• 作为试剂：
  描述：

  水 在 [(2,2'-bipyridine)2(H2O)Ru(III)ORu(III)(OH2)(2,2'-bipyridine)](4+) LiClO₄ 、 SiO₂ 作用下， 以 水 为溶剂， 生成 氧气
  参考文献：
  名称：

  在均相介质中和胶体SiO 2悬浮液中氧桥联钌配合物对水的催化氧化

  摘要：

  羰基桥接钌络合物[（bpy）2（H 2 O）RuORu（H 2 O）（bpy）2 ] 4+（bpy =联吡啶）催化O 2从水中逸出的速率取决于pH；将调光剂固定在SiO 2悬浮液上可以提高O 2的产率，但是会降低生产率。

  DOI：

  10.1039/c39840001635

文献信息

• Water Exchange Rates in the Diruthenium μ-Oxo Ion <i>cis,cis</i>-[(bpy)₂Ru(OH₂)]₂O⁴⁺
  作者：Hiroshi Yamada、Tohru Koike、James K. Hurst

  DOI：10.1021/ja010594l

  日期：2001.12.1

  intermediate accumulated during the course of the isotope exchange reaction that gave a [5,5] ion possessing both approximately 782 and approximately 812 cm(-1) bands; this spectrum was assigned to the mixed-isotope species, (bpy)(2)Ru((16)O)(16)ORu((18)O)(bpy)(2)(4+). Kinetic analysis of solutions at various levels of oxidation indicated that only the [3,3] ion underwent substitution; the exchange rate constant

  将 2 当量的 Ce(4+) 添加到二聚钌 mu-氧离子 cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+)（形式氧化态 III） -III，随后表示为 [3,3]) 或将 1 当量的 Ce(4+) 添加到相应的 [3,4] 离子中，几乎定量地转化为 [4,4] 离子，证实了我们最近的分配这种氧化态作为水氧化过程中由 cis,cis-[(bpy)(2)Ru(O)](2)O(4+) ([5,5]) 离子积累的中间体。通过将富含 H(2)(18)O 的样品在正常水中孵育预定时间，然后将其氧化，研究 [3,3] 和 [3,4] 离子中顺水位置处的水交换率到 [5,5] 状态并通过共振拉曼 (RR) 光谱测量在 780 和 818 cm(-1) 处 O 同位素敏感带的大小变化。这些带已分别指定为 Ru=(18)O 和 Ru=(16)O 拉伸模式，用于通过氧化成 [5,5] 状态
• The kinetics and mechanism of the oxidation of diaquotetrakis(2,2′-bipyridine)-μ-oxodiruthenium(III) ion by bromate in aqueous perchloric acid
  作者：Johnson Femi Iyun、Godwin Adefikayo Ayoko、Yilkur Nandul Lohdip

  DOI：10.1016/s0277-5387(00)83529-9

  日期：1992.1

  principal reactant bromate species. The reaction was mildly catalysed by anions in the order CH3COO− > NO3− $̆HCOO−. The activation parameters were determined at [H+] = 0.01 M as ΔH‡ = −9.6±0.3 kJ mol−1 and ΔS‡ = 112.9 ± 5.1 J mol−1 K−1 respectively. The observed anion catalysis, the Michaelis-Menten plot and the result of the spectroscopic investigation do not support a mechanism involving pre-electron-transfer

  在I = 1.0 M（NaClO 4），T = 25.0±0.1°C，0.01⩽[H + ]⩽0.20 M时，diaquotetrakis-（2,2'-bipyridine）-μ-oxo-diruthenium（III）的氧化离子（以下简称为RuORu 4+溴酸钾服从）的速率定律-d [RuORu 4+ ] / d吨= 5 [ ķ + ķ ħ [H + ] 2 ] [的BrO 3 - ] Ť [RuORu 4+ ] ，其中k =（6.50±0.10）×10 -2 M -1 s -1和k H = 2.67±0.28 M-3 š 1分别。发生由平行酸无关的，并且酸依赖性途径表明H中的反应2的BrO 3 +和的BrO 3 -作为主要反应物的溴酸盐物种。将反应物温和地通过阴离子以顺序CH催化3 COO - > NO 3 - $ HCOO - 。激活参数在[H + ] = 0.01 M时确定为ΔH ‡
• Mechanism of Water Oxidation by the μ-Oxo Dimer [(bpy)₂(H₂O)Ru^IIIORu^III(OH₂)(bpy)₂]⁴⁺
  作者：Robert A. Binstead、Chris W. Chronister、Jinfeng Ni、Chris M. Hartshorn、Thomas J. Meyer

  DOI：10.1021/ja993235n

  日期：2000.9.1

  The kinetics and mechanism of CeIV oxidation of the water oxidation catalyst [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ (1, RuIIIORuIII) have been investigated by UV−visible measurements with application of global analysis. The reaction proceeds by stepwise oxidation of RuIIIORuIII to RuVORuV with oxidation of RuIVORuIII the slow step. RuVORuV has been identified as an intermediate by the appearance of

  水氧化催化剂 [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ (1, RuIIIORuIII) 的 CeIV 氧化动力学和机理已通过紫外-可见测量和全局分析进行了研究。反应通过将 RuIIIORuIII 逐步氧化为 RuVORuV 进行，而 RuIVORuIII 的氧化是缓慢的步骤。RuVORuV 已被鉴定为中间体，因为其 ClO4-盐在 5 °C 的浓缩溶液中呈黑色悬浮液。它是水氧化的关键中间体。该机制可能涉及双分子步骤和过氧桥中间体的形成。由于 O2 析出引起的阳化，催化水氧化在仅仅几个催化循环后就大大延迟。
• Dobson, John C.; Sullivan, B. Patrick; Doppelt, Pascal, Inorganic Chemistry, 1988, vol. 27, # 21, p. 3863 - 3866
  作者：Dobson, John C.、Sullivan, B. Patrick、Doppelt, Pascal、Meyer, Thomas J.

  DOI：——

  日期：——
• Structure and Electronic Configurations of the Intermediates of Water Oxidation in Blue Ruthenium Dimer Catalysis
  作者：Dooshaye Moonshiram、Jonah W. Jurss、Javier J. Concepcion、Taisiya Zakharova、Igor Alperovich、Thomas J. Meyer、Yulia Pushkar

  DOI：10.1021/ja208636f

  日期：2012.3.14

  Catalytic O-2 evolution with cis,cis-[(bpy)(2)(H2O)-(RuORuIII)-O-III(OH2)(bpy)(2)](4+) (bpy is 2,2-bipyridine), the so-called blue dimer, the first designed water oxidation catalyst, was monitored by UV-vis, EPR, and X-ray absorption spectroscopy (XAS) with ms time resolution. Two processes were identified, one of which occurs on a time scale of 100 ms to a few seconds and results in oxidation of the catalyst with the formation of an intermediate, here termed [3,4]'. A slower process occurring on the time scale of minutes results in the decay of this intermediate and O-2 evolution. Spectroscopic data suggest that within the fast process there is a short-lived transient intermediate, which is a precursor of [3,4]'. When excess oxidant was used, a highly oxidized form of the blue dimer [4,5] was spectroscopically resolved within the time frame of the fast process. Its structure and electronic state were confirmed by EPR and XAS. As reported earlier, the [3,4]' intermediate likely results from reaction of [4,5] with water. While it is generated under strongly oxidizing conditions, it does not display oxidation of the Ru centers past [3,4] according to EPR and XAS. EXAFS analysis demonstrates a considerably modified ligand environment in [3,4]'. Raman measurements confirmed the presence of the O-O fragment by detecting a new vibration band in [3,4]' that undergoes a 46 cm(-1) shift to lower energy upon O-16/O-18 exchange. Under the conditions of the experiment at pH 1, the [3,4]' intermediate is the catalytic steady state form of the blue dimer catalyst, suggesting that its oxidation is the rate-limiting step.