trans-[RuCl₂(azpy)(CO)₂] | 1162683-04-6

• 英文名称: trans-[RuCl₂(azpy)(CO)₂]
• 英文别名: dicarbonyldichloro(2-phenylazopyridine)ruthenium(II)
• CAS: 1162683-04-6
• 化学式: C₁₃H₉Cl₂N₃O₂Ru
• 分子量: 411.209
• InChiKey: DEJQLSXUOZKDGH-ACQMDWLESA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 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：

  trans-[RuCl₂(azpy)(CO)₂] 以 二氯甲烷 为溶剂， 生成 一氧化碳
  参考文献：
  名称：

  Differences in the CO photolability of cis- and trans-[RuCl2(azpy)(CO)2] complexes: Effect of metal-to-ligand back-bonding

  摘要：

  Reaction of [RuCl2(CO)(3)](2) with 2-phenylazopyridine (azpy) in methanolic solution affords cis-[RuCl2(azpy)(CO)(2)] (1) and trans-[RuCl2(azpy)(CO)(2)] (2) depending on the temperature of the reaction mixture. In both complexes, the two CO ligands are cis to each other. Competition in pi backbonding labilizes CO trans to the azo-N (N-3) in 2 and increases the rate of CO photorelease of 2 (the trans isomer) compared to 1 (the cis isomer). (c) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2013.07.047
• 作为产物：
  描述：

  (E)-2-(phenyldiazenyl)pyridine 、 [Ru(CO)₃Cl₂(MeOH)] 以 甲醇 为溶剂， 反应 3.0h， 以65%的产率得到trans-[RuCl₂(azpy)(CO)₂]
  参考文献：
  名称：

  Differences in the CO photolability of cis- and trans-[RuCl2(azpy)(CO)2] complexes: Effect of metal-to-ligand back-bonding

  摘要：

  Reaction of [RuCl2(CO)(3)](2) with 2-phenylazopyridine (azpy) in methanolic solution affords cis-[RuCl2(azpy)(CO)(2)] (1) and trans-[RuCl2(azpy)(CO)(2)] (2) depending on the temperature of the reaction mixture. In both complexes, the two CO ligands are cis to each other. Competition in pi backbonding labilizes CO trans to the azo-N (N-3) in 2 and increases the rate of CO photorelease of 2 (the trans isomer) compared to 1 (the cis isomer). (c) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2013.07.047

文献信息

• Novel [Ru(polypyridine)(CO)2Cl2] and [Ru(polypyridine)2(CO)Cl]+-type complexes: Characterizing the effects of introducing azopyridyl ligands by electrochemical, spectroscopic and crystallographic measurements
  作者：Dai Oyama、Akio Asuma、Takashi Hamada、Tsugiko Takase

  DOI：10.1016/j.ica.2008.11.023

  日期：2009.6

  The reaction of ruthenium carbonyl polymer ([Ru(CO)(2)Cl-2](n)) with azopyridyl compounds (2,2'-azobispyridine; apy or 2-phenylazopyridine; pap) generated new complexes, [Ru(azo)(CO)(2)Cl-2] (azo = apy, pap). [Ru(apy)(CO)(2)Cl-2] underwent photodecarbonylation to give a chloro-bridged dimer complex, whereas the corresponding pap complex ([Ru(pap)(CO)(2)Cl-2]) was not converted to a dimer. The reactions of the chloro-bridged dimer containing the bpy ligand (bpy = 2,2'-bipyridine) with either apy or pap resulted in the formation of mixed polypyridyl complexes, [Ru(azo)(bpy)(CO)Cl](+). The novel complexes containing azo ligands were characterized by various spectroscopic measurements including the determination of X-ray crystallographic structures. Both [Ru(azo)(CO)(2)Cl-2] complexes have two CO groups in a cis position to each other and two chlorides in a trans position. The azo groups are situated cis to the CO ligand in [Ru(azo)(bpy)(CO)Cl](+). All complexes have azo N-N bond lengths of 1.26-1.29 angstrom. The complexes exhibited azo-based two-electron reduction processes in electrochemical measurements. The effects of introducing azopyridyl ligands to the ruthenium carbonyl complexes were examined by ligand-based redox potentials, stretching frequencies and force constants of CO groups and bond parameters around Ru-CO moieties. (C) 2008 Elsevier B.V. All rights reserved.