2,2'-bipyrimidine-bis(2,2'-bipyridine)ruthenium(II)(2+) | 65013-22-1

• 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'-bipyrimidine-bis(2,2'-bipyridine)ruthenium(II)(2+)
• 英文别名: bis(2,2'-bipyridine)(2,2'-bipyrimidine)ruthenium(II)(2+)；{Ru(bpy)2bpm}(2+)；[Ru(bpy)₂(2,2′-bipyrimidine)]；[Ru(bpy)₂(bpm)]；[Ru(II)(bpy)2(bpmH)](2+)；[Ru(bipy)2(bpm)](2+)；2-Pyridin-2-ylpyridine;2-pyrimidin-2-ylpyrimidine;ruthenium(2+)
• CAS: 65013-22-1；170553-54-5
• 化学式: C₂₈H₂₂N₈Ru
• 分子量: 571.606
• InChiKey: FLPJBLXDLPWXRM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2,2'-bipyrimidine-bis(2,2'-bipyridine)ruthenium(II)(2+) 以 乙腈 为溶剂， 生成 [Ru(II)(bpy)2(bpmH)](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(II)(bpy)2(bpmH)](1+) 在 methyl viologen⁽²⁺⁾ 作用下， 以 sodium hydroxide 为溶剂， 生成 2,2'-bipyrimidine-bis(2,2'-bipyridine)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

• A TiO2 immobilized Ru(ii) polyazine complex: a visible-light active photoredox catalyst for oxidative cyanation of tertiary amines
  作者：Pawan Kumar、Sanny Varma、Suman L. Jain

  DOI：10.1039/c3ta14783e

  日期：——

  nanocrystalline TiO2 grafted ruthenium(II) polyazine complex was found to be an efficient visible light photoredox catalyst for the oxidative cyanation of tertiary amines to the corresponding α-aminonitriles in high to excellent yields, using molecular oxygen as an oxidant and sodium cyanide in acetic acid as a cyanide source. The developed photoredox catalyst could be easily recovered by simple filtration

  发现化学功能化的纳米晶TiO 2接枝的钌（II）聚嗪络合物是一种高效的可见光光氧化还原催化剂，使用分子氧作为氧化剂和钠，可以将叔胺氧化氰化成相应的α-氨基腈，而且产率高至优异。乙酸中的氰化物为氰化物来源。所开发的光氧化还原催化剂可以通过简单的过滤容易地回收，并在具有恒定催化活性的情况下重复使用几次。
• Syntheses and photophysical properties of visible-light-absorbing Ru(II) polypyridyl complexes possessing (pyridylpyrazolyl)metal tethers
  作者：Tomohide Saita、Hiroyuki Nitadori、Akiko Inagaki、Munetaka Akita

  DOI：10.1016/j.jorganchem.2009.05.024

  日期：2009.9

  Novel Ru(II) polypyridyl complexes possessing pyridylpyrazolyl tethers were synthesized. Reactions with various organometallic precursors readily afforded multinuclear complexes which possess a light-harvesting Ru(II) core and (pyridylpyrazolyl) metal fragments in high yields. Analysis of the photophysical properties of the obtained multinuclear complexes revealed that the complexes had similar absorption and emission characteristics; however, their emission quantum yields decreased in proportion to the number of metal fragments. The di- and trinuclear complexes were stable under donating solvent such as CH3CN. (C) 2009 Elsevier B.V. All rights reserved.
• 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.
• Diastereoisomeric forms of ligand-bridged dimetallic diruthenium(<scp>II</scp>) and ruthenium(<scp>II</scp>)–osmium(<scp>II</scp>) species containing bidentate polypyridyl ligands
  作者：David A. Reitsma、F. Richard Keene

  DOI：10.1039/dt9930002859

  日期：——

  A new general synthetic route is reported for dinuclear species of the type [(L(t))2RuL(b)Ru(L)'2]4+ or [(L(t))2RuL(b)Os(L(t)')2]4+ (L(t), L(t)' = bidentate polypyridyl ligands, L(t), not-equal L(t)'; L(b) = bridging ligand), together with the chromatographic separation and characterization of the diastereoisomeric pairs of the dimers.