[(2,4-pentanedionato)2Ru(2,2'-azobis(pyridine))] | 1015227-59-4

• 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: [(2,4-pentanedionato)2Ru(2,2'-azobis(pyridine))]
• 英文别名: [Ru(2,4-pentanedionato)2(2,2'-azobispyridine)]；[(acetylacetonato)2Ru(2,2'-azobis(pyridine))]；[Ru(acac)2(abpy)]
• CAS: 1015227-59-4
• 化学式: C₂₀H₂₂N₄O₄Ru
• 分子量: 483.489
• InChiKey: NQHWERQFIFJLJE-VPOCKCTCSA-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：

  ammonium hexafluorophosphate 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 [(2,4-pentanedionato)2Ru(2,2'-azobis(pyridine))] 以 乙醇 、 水 为溶剂， 以69%的产率得到[(acetylacetonato)2Ru(μ-2,2'-azobis(pyridine))Ru(p-cymene)Cl]PF6
  参考文献：
  名称：

  氧化还原活性配体桥接的不对称二钌络合物

  摘要：

  不对称双核络合物[（acac）2 Ru1（μ-abpy）Ru2（Cym）Cl] PF 6（[ 2 ] PF 6），acac – =乙酰丙酮= 2,4-戊二酮，abpy = 2,2'-从单核前体[Ru（acac）2（abpy）]和[Ru（Cym）Cl 2 ] 2获得了偶氮二（吡啶）和Cym =对-cymene = 1-异丙基-4-甲基苯。X射线晶体结构分析表明氧化态制剂[（ACAC）2 RU1 III（μ-abpy • -）RU2 II（CYM）CL] +为2 +，在一个Ru III中心与自由基-阴离子桥联配体（abpy •–）之间进行反铁磁耦合，基于1.352（3）Å的N–N距离。作为适当的参考，新合成的单核[（abpy）Ru II（Cym）Cl] PF 6（[ 1 ] PF 6）在d（NN）= 1.269（4）Å时具有未还原的N═N双键双核[（acac）2 Ru 2.5（μ-abpy •–）Ru

  DOI：

  10.1021/ic201975h
• 作为产物：
  描述：

  (E)-二(吡啶-2-基)二氮烯 、 bis(acetonitrile)bis(2,4-pentanedionato)ruthenium(II) 以 乙醇 为溶剂， 以20%的产率得到[(2,4-pentanedionato)2Ru(2,2'-azobis(pyridine))]
  参考文献：
  名称：

  Mixed-Valent Metals Bridged by a Radical Ligand:  Fact or Fiction Based on Structure-Oxidation State Correlations

  摘要：

  Electron-rich Ru(acaC)(2) (acac(-) = 2,4-pentanedionato) binds to the pi electron-deficient bis-chelate ligands L, L = 2,2'-azobispyridine (abpy) or azobis(5-chloropyrimidine) (abcp), with considerable transfer of negative charge. The compounds studied, (abpy)Ru(acac)(2) (1), meso-(mu-abpy)[Ru(acaC)(2)](2) (2), rac-(mu-abpy)[Ru(acac)(2)](2) (3), and (mu-abcp)[Ru(acac)(2)](2) (4), were calculated by DFT to assess the degree of this metal-to-ligand electron shift. The calculated and experimental structures of 2 and 3 both yield about 1.35 angstrom for the length of the central N-N bond which suggests a monoanion character of the bridging ligand. The NBO analysis confirms this interpretation, and TD-DFT calculations reproduce the observed intense long-wavelength absorptions. While mononuclear 1 is calculated with a lower net ruthenium-to-abpy charge shift as illustrated by the computed 1.30 angstrom for d(N-N), compound 4 with the stronger pi accepting abcp bridge is calculated with a slightly lengthened N-N distance relative to that of 2. The formulation of the dinuclear systems with monoanionic bridging ligands implies an obviously valence-averaged (RuRuII)-Ru-III mixed-valent state for the neutral molecules. Mixed valency in conjunction with an anion radical bridging ligand had been discussed before in the discussion of MLCT excited states of symmetrically dinuclear coordination compounds. Whereas 1 still exhibits a conventional electrochemical and spectroelectrochemical behavior with metal centered oxidation and two ligand-based one-electron reduction waves, the two one-electron oxidation and two one-electron reduction processes for each of the dinuclear compounds Ru-2.5(L*(-))Ru-2.5 reveal more unusual features via EPR and UV-vis-NIR spectroelectrochemistry. In spite of intense near-infrared absorptions, the EPR results show that the first reduction leads to Ru-II(L*(-))Ru-II species, with an increased metal contribution for system 4*(-). The second reduction to Ru-II(L2-)Ru-II causes the disappearance of the NIR band. One-electron oxidation of the Ru-2.5(L*(-)) Ru-2.5 species produces a metal-centered spin for which the alternatives Ru-III(L-0)Ru-II or Ru-III(L*(-))Ru-III can be formulated: The absence of NIR bands as common for mixed-valent species with intervalence charge transfer (IVCT) absorption favors the second alternative. The second one-electron oxidation is likely to produce a dication with Ru-III(L-0)Ru-III formulation. The usefulness and limitations of the increasingly popular structure/oxidation state correlations for complexes with noninnocent ligands is being discussed.

  DOI：

  10.1021/ja077676f