2-吡嗪-2-基吡嗪钌(2+) | 150199-60-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 中文名称: 2-吡嗪-2-基吡嗪钌(2+)
• 英文名称: tris(bipyrazine)ruthenium(II)
• 英文别名: tris(2,2'-bipyrazine)ruthenium(II)(2+)；[Ru(2,2'-bipyrazine)3](2+)；{Ru(2,2'-bipyrazine)3}(2+)；Ru(2,2'-bipyrazine)3(2+)；[Ru(2,2′-bipyrazine)₃]²⁺；[ruthenium(II)(2,2′-bipyrazyl)3](2+)；2-Pyrazin-2-ylpyrazine;ruthenium(2+)；2-pyrazin-2-ylpyrazine;ruthenium(2+)
• CAS: 150199-60-3；75523-96-5
• 化学式: C₂₄H₁₈N₁₂Ru
• 分子量: 575.557
• InChiKey: LGAFSIQNRRRLLT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  37
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  155
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2-吡嗪-2-基吡嗪钌(2+) 以 乙腈 为溶剂， 生成 tris(2,2'-bipyrazine)ruthenium(1+)
  参考文献：
  名称：

  同型和杂配型单核和双核三（α-二亚胺）钌自由基配合物的 ESR

  摘要：

  11 个单核和 5 个双核单还原三（{α}-二亚胺）钌（II）配合物的综合 ESR 研究通式 ((L){sub 3}Ru){sup {sm bullet}+}, (( L)(bpy){sub 2}Ru){sup {sm bullet}+}, and ((bpy){sub 2}Ru({mu}-L)Ru(bpy){sub 2}){sup {sm bullet}3+}（bpy, 2,2{prime},-bipyridine; L, other {alpha}-diimine）显示各种 g 因子和光谱分辨率。所有顺磁性物质都是真正的阴离子-自由基复合物，g 各向异性很小，g（配体自由基）- g（复合物）相对较小但具有正差异。这些变化与配体的计算性质以及抗磁性前体复合物的光谱和电化学数据相关。特别是，g 位移取决于 (i) 金属-配体相互作用的程度和 (ii) 单独占据和相邻未占据或完全填充轨道之间

  DOI：

  10.1021/ja00157a028
• 作为产物：
  描述：

  tris(2,2'-bipyrazine)ruthenium(1+) 在 methyl viologen⁽²⁺⁾ 作用下， 以 sodium hydroxide 为溶剂， 生成 2-吡嗪-2-基吡嗪钌(2+)
  参考文献：
  名称：

  钌（II）-二亚胺络合物的单电子还原：水溶液中含有2,2'-联吡啶，2,2'-联嘧啶和2,2'-联吡嗪的还原物种的表征

  摘要：

  The one-electron reductions of ten Ru(II)-diimine complexes of the general formula Ru(bpy)3-m-z(bpm)m(bpz)z2+ (bpy = 2,2'-bipyridine, bpm = 2,2'-bipyrimidine, bpz = 2,2'-bipyrazine, m and z = 0,1,2,3 and m + z less-than-or-equal-to 3), generically indicated as RuL2+, have been investigated in aqueous solution by the use of radiation chemical and electrochemical techniques, leading to the characterization of the one-electron reduced products (RuL.+) and their conjugate acids (RuLH.2+). Because the ease of reduction of the ligands follows the trend bpz > bpm > bpy, the electron added to RuL2+ is localized on the ligand that is most easily reduced. The E-degrees values for the RuL2+/RuL.+ couples range from -0.50 V to -1.22 V for Ru(bpz)3(2+) and Ru(bpy)3(2+), respectively. All the RuL.+ absorption spectra show intense bands (epsilon-max approximately 10(4) M-1 cm-1) in the 340- and 480-nm regions that arise from ligand-localized transitions within the uniquely reduced ligand, with the visible band also overlapped by a MLCT band; the absorption bands of RuLH.2+ are shifted somewhat to the blue. From the variation of the absorbance as a function of pH, the pK(a) values of RuLH.2+ are obtained; they range from 6.3 to 9.2 for Ru(bpm)2(bpmH.-)2+ to Ru(bpy)2(bpzH.-)2+, respectively, and correlate linearly with E-degrees (RuL2+/RuL.+), with separate lines for bpz and bpm acceptor ligands. From the values of pK(a) and E-degrees (RuL2+/RuL.+), E-degrees (RuL2+,H+/RuLH.2+) are obtained. The rate constants for the following electron-transfer reactions have been measured or calculated and have been correlated with the values of DELTA-G-degrees and other kinetic parameters by use of the Marcus theory: RuL2+ +.CO2- --> RuL.+ + CO2, RuL.+ + MV2+ --> RuL2+ + MV.+ and its reverse reaction, and RuLH.2+ + MV2+ --> RuL2+ + MV.+ + H+ and its reverse reaction. The relevance of the results to the use of the complexes as electron-transfer photosensitizers is discussed.

  DOI：

  10.1021/j100166a040
• 作为试剂：
  描述：

  二氧化碳 在 钌 2-吡嗪-2-基吡嗪钌(2+) 、 三乙醇胺 、 水 、 氢气 作用下， 以 水 为溶剂， 生成 methane
  参考文献：
  名称：

  使用可见光将水溶液中的二氧化碳光还原为甲烷

  摘要：

  通过太阳光将 CO/sub 2/ 还原为可燃有机产品，作为太阳能转换和存储的一种手段具有重要意义。最近已经针对光诱导的 CO/sub 2/-固定过程的发展进行了认真的尝试。已经报道了使用均相催化剂、半导体颗粒或人工酶催化耦合系统将 CO/sub 2/ 还原为一氧化碳、甲酸盐和其他有机酸。将CO/sub 2/ 还原为甲烷，甲烷化过程CO/sub 2/ + 4H/sub 2/ ..-->.. CH/sub 4/ + 2H/sub 2/O 具有重要的工业重要性。该反应在高温高压下进行，由Ru、Mo、Ni等金属催化剂催化。已经报道了使用 Ru 电极电催化还原 CO/sub 2/。

  DOI：

  10.1021/ja00285a043

文献信息

• Protonation Studies of Reduced Ruthenium(II) Complexes with Polypyridyl Ligands
  作者：Peter A. Anderson、Robert F. Anderson、Masaoki Furue、Peter C. Junk、F. Richard Keene、Bradley T. Patterson、Brett D. Yeomans

  DOI：10.1021/ic991070d

  日期：2000.6.1

  The pKa values associated with protonation of the one-electron reduced forms of series of [L'2Ru(II)L]2+ complexes [L' = bidentate polypyridyl ligand; L = bidentate polypyridyl ligand with additional uncoordinated N atoms in the aromatic ring system: e.g., dpp = 2,3-bis(2-pyridyl)pyrazine, bpz = 2,2'-bipyrazine] were assessed using pulse radiolysis techniques by the measurement of spectral variations

  与一系列[L'2Ru（II）L] 2+配合物的单电子还原形式的质子化相关的pKa值[L'=双齿多吡啶基配体；L =芳族环系统中带有其他未配位N原子的双齿聚吡啶基配体：例如，使用脉冲辐射分解技术通过测量评估了dpp = 2,3-双（2-吡啶基）吡嗪，bpz = 2,2'-联吡嗪]光谱变化与pH的关系。对于其中可质子化的配体同时是还原位点的复合物，在pKa和E之间观察到线性相关性（RuL'2L2 + / +）。在一个或多个不可质子化的配体（L'）具有非常低的pi *能级[例如（CF3）4bpy]的配合物中，不可质子化的配体发生还原，并且观察到还原物种的pKa值显着降低。
• Venturi, Margherita; Mulazzani, Quinto G.; Ciano, Mauro, Inorganic Chemistry, 1986, vol. 25, # 25, p. 4493 - 4498
  作者：Venturi, Margherita、Mulazzani, Quinto G.、Ciano, Mauro、Hoffman, Morton Z.

  DOI：——

  日期：——
• Temperature dependence of the electrogenerated chemiluminescence efficiency of Ru(bpz)32+ in acetonitrile. A mechanistic interpretation
  作者：Jaime Gonzalez-Velasco

  DOI：10.1021/j100319a024

  日期：1988.4
• Protonation of the ground states of ruthenium(II) photosensitizers
  作者：Alessandro Rugge、Catherine D Clark、Morton Z Hoffman、D.Paul Rillema

  DOI：10.1016/s0020-1693(98)00124-8

  日期：1998.10

  Ru(II) complexes that possess 2,2'-bipyrazine, 2,2'-bipyrimidine, and 2-(2'-pyridyl)pyrimidine ligands in combination with 2,2'-bipyridine undergo protonation at the basic nitrogen heteroatoms on the periphery of the aromatic rings as the solution is made more acidic, resulting in changes in the absorption spectra. In this study, the acidity of the solution was controlled with concentrated H2SO4; titration curves for the first protonations were obtained from plots of absorbance versus acidity, from which the pK(a1) values for the monoprotonated species were extracted. As has been observed before for the acid-base properties of the excited states and the one-electron reduced forms of the complexes, the pK(a1) values of the protonated forms of the ground states (- 1.6 to - 5.0) correlate with the reduction potentials, and demonstrate site selectivity of the protonation process. (C) 1998 Elsevier Science S.A. All rights reserved.
• Reductive quenching of the luminescent excited state of tris(2,2'-bipyrazine)ruthenium(2+) ion in aqueous solution
  作者：Gilda Neshvad、Morton Z. Hoffman

  DOI：10.1021/j100343a044

  日期：1989.3