(ethylenediaminetetraacetato)(oxo)ruthenium(V) | 133267-33-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (ethylenediaminetetraacetato)(oxo)ruthenium(V)
• 英文别名: [Ru(V)(ethylenediaminetetraacetate(4-))O](1-)；[(ethylenediaminetetraacetato)Ru(=O)](1-)；[O=Ru(ethylenediaminetetraacetate)](1-)；[(edta)Ru(=O)](1-)
• CAS: 133267-33-1
• 化学式: C₁₀H₁₂N₂O₈*ORu
• 分子量: 405.283
• InChiKey: FNLGFRSIWWHLRS-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -7.53
• 重原子数：
  22.0
• 可旋转键数：
  11.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  184.07
• 氢给体数：
  0.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (ethylenediaminetetraacetato)(oxo)ruthenium(V) 在 三苯基膦 作用下， 生成 aquo-ethylenediaminetetraacetato ruthenate(III) 、 三苯基氧化膦
  参考文献：
  名称：

  Taqui Khan, M. M.; Chatterjee, D.; Samad, S. A., Journal of Molecular Catalysis, 1990, vol. 61, p. 55 - 60

  摘要：

  DOI：
• 作为产物：
  描述：

  aquo-ethylenediaminetetraacetato ruthenate(III) 在 sodium hypochlorite 作用下， 生成 (ethylenediaminetetraacetato)(oxo)ruthenium(V)
  参考文献：
  名称：

  Taqui Khan, M. M.; Chatterjee, D.; Samad, S. A., Journal of Molecular Catalysis, 1990, vol. 61, p. 55 - 60

  摘要：

  DOI：

文献信息

• Kinetics and mechanism of the [RuIII(edta)(H2O)]−-mediated oxidation of cysteine by H2O2
  作者：Debabrata Chatterjee、Erika Ember、Ujjwal Pal、Sarita Ghosh、Rudi van Eldik

  DOI：10.1039/c1dt10623f

  日期：——

  The kinetics and mechanism of the [RuIII(edta)(H2O)]−-mediated oxidation of cysteine (RSH) by hydrogen peroxide (edta4− = ethylenediaminetetraacetate), were studied in detail as a function of both the hydrogen peroxide and cysteine concentrations at pH 5.1 and room temperature. The kinetic traces reveal clear evidence for a catalytic process in which hydrogen peroxide reacts directly with cysteine coordinated to the RuIII(edta) complex in the form of [RuIII(edta)SR]2−. A parallel process in which [RuIII(edta)(H2O)]− first reacts with H2O2 to produce [RuV(edta)O]− and subsequently oxidizes cysteine, is orders of magnitude slower than the [RuIII(edta)(H2O)]−-mediated oxidation in which cysteine rapidly coordinates to [RuIII(edta)(H2O)]− prior to the reaction with H2O2. HPLC product analyses revealed the formation of cystine (RSSR) as major product along with cysteine sulfinic acid (RSO2H) in the reaction system, and established the catalytic role of [RuIII(edta)(H2O)]−. Simulations were performed to account for the rather complex kinetic traces in terms of the suggested reaction mechanism. The results of the simulations support the proposed reaction mechanism that involves the oxidation of coordinated cysteine to cysteine sulfenic acid (RSOH), which subsequently rapidly reacts with H2O2 and RSH to form RSO2H and RSSR, respectively.

  详细研究了[RuIII(edta)(H2O)]-介导的过氧化氢（edta4-=乙二胺四乙酸）氧化半胱氨酸（RSH）的动力学和机制，作为过氧化氢和乙二胺四乙酸的函数。 pH 5.1 和室温下的半胱氨酸浓度。动力学痕迹揭示了催化过程的清晰证据，其中过氧化氢直接与以 [RuIII(edta)SR]2- 形式配位到 RuIII(edta) 复合物的半胱氨酸反应。 [RuIII(edta)( )]→ 首先与 2 反应生成 [RuV(edta)O]→ 并随后氧化半胱氨酸的并行过程比 [RuIII(edta) 慢几个数量级( )]‐介导的氧化反应，其中半胱氨酸在与 2 反应之前快速与 [RuIII(edta)( )]‐ 配位。 HPLC 产物分析表明，反应体系中主要产物为胱氨酸 (RSSR) 和半胱氨酸亚磺酸 (RSO2H)，并确定了 [RuIII(edta)( )] 的催化作用。进行模拟以解释所建议的反应机制中相当复杂的动力学轨迹。模拟结果支持了所提出的反应机制，其中涉及配位半胱氨酸氧化为半胱氨酸磺酸（RSOH），随后与 2和RSH快速反应，分别形成RSO2H和RSSR。
• Kinetics and mechanism of the reaction of [Ru^III(edta)(H₂O)]⁻with HOBr to form an intermediate Ru^VO complex in aqueous solution
  作者：Debabrata Chatterjee、Anannya Mitra、Rudi van Eldik

  DOI：10.1039/b604473e

  日期：——

  The interaction of [RuIII(edta)(H2O)]− (1) (edta = ethylenediaminetetraacetate) with the oxygen transfer agent HOBr, was studied kinetically as a function of [HOBr] and temperature (5–35 °C) at a fixed pH of 6.2. Spectroscopic evidence is reported for the formation of a high valent intermediate (edta)RuVO complex. Water soluble 2,2′-azobis(3-ethylbenzithiazoline-6-sulfonate) (ABTS) was employed as

  [Ru III（edta）（H 2 O）] -（1）（edta =乙二胺四乙酸酯）与氧气转移剂HOBr的相互作用是动力学研究的，是[HOBr]和温度（5-35°C）的函数在6.2的固定pH下。报道了形成高价中间体（edta）Ru V O络合物的光谱学证据。水为了获得更多的机理信息，可溶的2,2'-偶氮双（3-乙基苯并噻唑啉-6-磺酸盐）（ABTS）被用作该中间体的捕集阱。在[ABTS]≫ [HOBr]≫ [ 1 ]的伪优先条件下进行反应，并根据时间监控其形成单电子氧化产物ABTS˙ +的过程。报告的动力学数据根据建议的反应机理进行解释，并参考之前报告的数据进行讨论。
• Kinetics and mechanism of O–O bond cleavage in the reaction of [RuIII(edta)(H2O)]− with hydroperoxides in aqueous solution
  作者：Debabrata Chatterjee、Anindita Sikdar、Vidya R. Patnam、Alexander Theodoridis、Rudi van Eldik

  DOI：10.1039/b803181a

  日期：——

  reaction of 1 with the hydroperoxides (t)BuOOH and KHSO(5), the common mechanism is one of heterolytic scission of the O-O bond. The water soluble and easy to oxidize substrate 2,2'-azobis(3-ethylbenzithiazoline-6-sulfonate (ABTS), was employed to substantiate the mechanistic proposal. Reactions were carried out under pseudo-first order conditions for [ABTS] >> [hydroperoxide] >> [1], and were monitored

  [Ru（III）（edta）（H（2）O）]（-）（1）（edta =乙二胺四乙酸盐）与叔丁基氢过氧化物（（t）BuOOH）和过硫酸氢钾（KHSO（5））的反应为研究人员使用停止流技术在固定pH值为6.1的条件下动力学研究了氧化剂浓度和温度（10-30摄氏度）的函数。通过使用整体动力学分析技术来分析动力学结果。发现该反应由两个步骤组成，涉及快速形成[Ru（III）（edta）（OOR）]（2-）中间体，该中间体随后进行溶解裂解形成[（edta）Ru（V）= O ]（-）。由于[EDRu（V）= O]（-）在1与氢过氧化物（t）BuOOH和KHSO（5）的反应中几乎是定量生成的，因此常见的机理是OO键的杂合断裂。水溶性且易氧化的底物2,2'
• Mechanism of the oxidation of thiosulfate with hydrogen peroxide catalyzed by aqua-ethylenediaminetetraacetatoruthenium(III)
  作者：Debabrata Chatterjee、Sanchari Shome、Namita Jaiswal、S.C. Moi

  DOI：10.1016/j.molcata.2014.01.029

  日期：2014.5

  Catalytic ability of [Ru-lll(edta)(H2O)](-) (edta(4-) = ethylenediaminetetraacetate) complex toward oxidation of thiosulfate (S2O32-) in presence of H2O2 has been explored in the present work. The kinetics of the catalytic oxidation of thiosulfate (S2O32-) has been studied spectrophotometrically as a function of [Rulll(edta)], [H2O2], [S2O32-] and pH. Spectral analyses and kinetic data indicate a catalytic pathway involving activation of both substrate (S2O32-) and oxidant (H2O2). Substrate activation pathway involves the formation of a red [Ru-lll(edta)(S2O3)](3-) species through the reaction of the [Ru-lll(edta)(H2O2)](-) catalyst complex and the substrate (S2O32-). Hydrogen peroxide reacts directly with thiosulfate coordinated to the Rum(edta) complex to yield sulfite as immediate oxidation product. Peroxide activation pathway is governed by the formation of [Ru-v(edta)(0)](-) catalytic intermediate which oxidize thiosulfate, however, at slower rate (k(ox)(2) = 0.012 M-1 s(-1) at 25 degrees C) as compared to the rate of oxidation of the coordinated thiosulfate (K-ox(1) = 0.93 M-1 s(-1) at 25 degrees C). Sulfite and sulfate were found to be the oxidation products of the above described catalytic oxidation process. A detailed mechanism in agreement with the spectral and kinetic data is presented. (C) 2014 Elsevier B.V. All rights reserved.
• Chatterjee, Debabrata; Padhiyar, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1997, vol. 36, # 11, p. 956 - 958
  作者：Chatterjee, Debabrata、Padhiyar

  DOI：——

  日期：——