[Ru(II)(N-(hydroxyethyl)ethylenediaminetriacetate)(D2O)](1-) | 763906-59-8

• 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: [Ru(II)(N-(hydroxyethyl)ethylenediaminetriacetate)(D2O)](1-)
• CAS: 763906-59-8
• 化学式: C₁₀H₁₅N₂O₇*H₂O*Ru
• 分子量: 396.308
• InChiKey: KVAFFWKPMDSFNH-ZSJDYOACSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -6.99
• 重原子数：
  21.0
• 可旋转键数：
  11.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  178.6
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  2-甲基吡嗪 、 [Ru(II)(N-(hydroxyethyl)ethylenediaminetriacetate)(D2O)](1-) 以 重水 为溶剂， 生成 Ru(N-hydroxyethylethylenediamine-N,N',N'-triacetate)(N-methylpyrazine)(1-)
  参考文献：
  名称：

  A Proton-Induced N-1 to η² Migration of the Fluxional Pyrazine in the [Ru^II(hedta)(pz)]^- Complex

  摘要：

  [Ru-II(hedta)(D2O)](-), hedta(3-) = N-(hydroxyethyl)ethylenediaminetriacetate, reacts with pyrazine in D2O at 25 degrees C to yield several isomers and less than or equal to 20% of the pyrazine-bridged binuclear complex. Two isomers of 56.2% combined abundance have differentiated alpha (near) and beta (remote) H-1 NMR pyrazine resonances at 9.09 ppm (alpha or H2, H6 pair) and 8.33 ppm (beta or H3, H5 pair). The other isomer of ca. 24% abundance exhibits only a singlet at 8.76 ppm, indicative of fluxional pyrazine movement from N-1 to N-4. This is believed to be the cis-polar isomer. Within 24 h the differentiated isomers convert to the fluxional isomer, which remains fluxional in 50% D2O/50% CD3OD down to 237 K. The fluxional isomer has all equivalent C-13 NMR resonances at 152.44 ppm, 5.18 ppm downfield of free pyrazine. Comparison with the bridged binuclear ion {[Ru(hedta)](2)(pz)}(2-) revealed fortuitously similar shifts; the H-1 NMR spectrum shows a singlet at 8.76 ppm, and the C-13 NMR spectrum, a singlet at 152.40 ppm. These species have different electrochemical signatures, however, with the 1:1 fluxional complex having a Ru-II/III wave at 0.20 V that shifts to 0.35 V upon protonation of the N-4 position, whereas the binuclear complex has two waves at 0.18 and 0.33 V which are independent of pH. H-1 NMR indicates stereochemically rigid coordination of 2-methylpyrazine (2-CH(3)pz) at N-4 with the 2-CH3 position remote in the major species (65.5%) and at N-2 with the 2-CH3 site adjacent (34.4%) in the lesser isomer. The proton resonances are as follows. Remote isomer (N-4): H2, 8.22 ppm; H3, 8.97 ppm; H5, 8.88 ppm; CH3, 2.53 ppm. Adjacent (N-1) isomer: H2, 8.73 ppm; H3, 8.42 ppm, H5, 8.50 ppm; CH3, 2.45 ppm. A slow conversion of the strained adjacent isomer to the remote isomer is observed. Remote and adjacent isomers were also prepared for [(NH3)(5)Ru(2-CH(3)pz)](2+) in 87.7% and 12.3% yield. Protonation of [Ru(hedta)(pz)](-) yields nonfluxional complexes: a major species (63%) bound eta(2)(1,2) With four complicated resonance patterns at 8.72, 8.57, 8.00, and 7.91 ppm, each signal having across-the-ring couplings which require couplings to at least two different ring protons and a minor N-1-coordinated N-4 protonated species (16%) with alpha and beta proton pairs resonating at 8.81 and 8.25 ppm. An eta(2)-(2,3) isomer is also detectable (20%) which has four types of H-1 resonances at 9.51, 9.01, 8.85, and 8.15 ppm. The weakened sigma bonding from pzH(+) and enhanced pi-acceptor capacity power of pzH(+) combine to induce a switch in coordination to either eta(2)(1,2) or eta(2)(2,3).

  DOI：

  10.1021/ic961269f

文献信息

• Stereochemically-rigid and fluxional pyrimidines within the bis-[Ru(hedta)(pym)2]− complex
  作者：Ya Chen、Fu-Tyan Lin、Rex E. Shepherd

  DOI：10.1016/s0020-1693(97)05759-9

  日期：1998.2

  stereochemically-rigid, exhibiting resonances at 9.25 (H2), 8.82 (H6), 8.68 (H4) and 7.45 (H5) ppm, respectively. The second pyrimidine is fluxional with rapid migration of the RuII center between N-1 and N-3 sites. This motion interchanges the H4 and H6 protons which resonate at 8.82 ppm; the H2 resonance appears at 9.15 ppm and H5 at 7.61 ppm. The weaker bonding exhibited by the fluxional pyrimidine also allows

  摘要双嘧啶配合物[RuII（hedta）（pym）2]-的形成是通过在[RuII（hedta）（H2O）]-中依次添加pym来实现的（hedta3- = N-羟乙基乙二胺三乙酸盐； pym =嘧啶）。第二步受到hedta3-配体的平面内羧基供体解离的速率限制；在22°C下k = 1.57×10−4 s-1。在0.10 M NaCl中，T = 22°C时，RuII / III波的E1 / 2值对于[RuII（hedta）（pym）]-为0.18 V，对于[RuII（hedta）（pym）2]-为0.54V。后者类似于二齿的2,2'-联吡啶复合物[Ru（hedta）（bpy）]-，其E1 / 2 = 0.48 V，说明了两个配位的N-杂环π-受体配体的影响。[RuII（hedta）（pym）2]-配合物的1 H NMR光谱揭示了两个结合的嘧啶的配位行为有所不同。一种嘧啶是立体化学刚性的，分别在9
• An asymmetrically-coordinated 2,3-dimethylpyrazine bridging ligand in the (II,II) binuclear ion, {[RuII(hedta)]2(2,3-Me2pz)}2− (hedta3− = N-hydroxyethylethylenediaminetriacetate)
  作者：Ya Chen、Rex E. Shepherd

  DOI：10.1016/s0020-1693(97)05758-7

  日期：1998.2

  [Ru(hedta)(H2O)]− (hedta3− = N-hydroxyethylethylenediaminetriacetate) reacts with 2,3-Me2pz (2,3-dimethylpyrazine) at 1:1, forming [Ru(hedta)(2,3-Me2pz)]− (1), and at 2:1, forming [Ru(hedta)]2(2,3-Me2pz)2− (2). Complex 1 is characterized by a RuII/III wave at 0.20 V versus NHE which shifts to 0.31 V upon protonation at N-4. Complex 2 exhibits two waves at 0.19 and 0.27 V from which the corrected comproportionation

  [Ru（hedta）（H 2 O）] -（hedta 3- = N-羟乙基乙二胺三乙酸酯）与2,3-Me 2 pz（2,3-二甲基吡嗪）以1：1反应，形成[Ru（hedta）（2 ，3-Me 2 pz）] -（1），并在2：1处形成[Ru（hedta）] 2（2,3-Me 2 pz）2-（2）。配合物1的特征是在相对于NHE的0.20 V时的Ru II / III波，在N-4质子化时，Ru II / III波变为0.31V。配合物2在0.19和0.27 V处表现出两个波，从该波中校正的匀称常数K c计算出``= 5.7''。K c ′的值表明Ru II / III中心之间的电子耦合非常差。[Ru（hedta）] 2（pz）} -络合物从190的K c ′值减小的根源是根据（i）由于2,3-旋转受阻而引起的轨道重叠差异而讨论的Me 2 pz配合物与pz情况的比较，或（ii）这些配合物中结
• ¹⁵N NMR and Electrochemical Studies of [Ru^II(hedta)]^- Complexes of NO, NO⁺, NO₂^-, and NO^-
  作者：Ya Chen、Fu-Tyan Lin、Rex E. Shepherd

  DOI：10.1021/ic980868e

  日期：1999.3.1

  The (15)N resonances appear at 260.0 ppm for the (15)NO(+) ligand and at 348.8 ppm for the bound (15)NO(2)(-) ligand in the [Ru(II)(hedta)((15)NO(2)(-))((15)NO(+))(D(2)O)] complex. Differential pulse voltammetric waves for the [Ru(II)(hedta)L](n)()(-) series occur at -0.37 V for the Ru(II)(NO(-))/Ru(II)(NO) couple, at -0.10 V for the Ru(II)(NO)/Ru(II)(NO(+)) couple, and at +0.98 V for the Ru(II)(NO(+))/Ru(III)(NO(+))

  [Ru（II）（hedta）L]（n）（）（-）配合物（hedta（3）（-）= N-（羟乙基）乙二胺三乙酸酯； L = NO（+），n = 0； L = NO， n = 1； L = NO（-），n = 2）是通过H（2）O / D（2）O通过NO（g）或NO（2）（-）置换而制备的。这是第一个报告的整套NO（+），NO和NO（-）化合物，它们是在恒定氧化态和恒定配体环境（此处为Ru（II）和氨基羧酸盐hedta（ 3）（-））。从离析盐的NO扩展频率来看，Ru（II）的反向捐赠及其sigma-drawing的净影响是，观察到NO（+）配合物的键序实际上是相同的（约2.46）。就像NO配合物（约2.48）一样。对NO（-）的背向赠与也很小，对NO（-）的背向赠与也很小，但是NO（-）和Ru（II）的轨道混合对于诱导单重态NO（-）络合物足够重要。（14）N-和（15）N-标记的复合物的n