tris(2,2'-bipyrimidine)ruthenium(II)(2+) | 80263-32-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: tris(2,2'-bipyrimidine)ruthenium(II)(2+)
• 英文别名: Ru(2,2'-bipyrimidine)3(2+)；[Ru(2,2'-bipyrimidine)3](2+)；[Ru(bpm)3](2+)；Ru(bpm)3(2+)；2-pyrimidin-2-ylpyrimidine;ruthenium(2+)
• CAS: 80263-32-7
• 化学式: C₂₄H₁₈N₁₂Ru
• 分子量: 575.557
• InChiKey: ZCWZXOGWEFPPNJ-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：
  0
• 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：

  tris(2,2'-bipyrimidine)ruthenium(II)(2+) 以 乙腈 为溶剂， 生成 Ru(bpm)3(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：

  Ru(2,2'-bipyrimidine)3H(2+) 在 methyl viologen⁽²⁺⁾ 作用下， 以 硫酸 为溶剂， 生成 tris(2,2'-bipyrimidine)ruthenium(II)(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

文献信息

• One-electron reduction of tris(2,2'-bipyrimidine)ruthenium(2+) ion in aqueous solution: a photochemical, radiation chemical, and electrochemical study
  作者：Gilda Neshvad、Morton Z. Hoffman、Quinto G. Mulazzani、Margherita Venturi、Mauro Ciano、Mila D'Angelantonio

  DOI：10.1021/j100353a028

  日期：1989.8
• 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.