[Ru(1,4,7-trithiacyclononane)(1,2-diaminoethane)(H2O)](2+) | 875275-03-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [Ru(1,4,7-trithiacyclononane)(1,2-diaminoethane)(H2O)](2+)
• 英文别名: ruthenium(II) aquo (1,4,7-trithiacyclononane)(ethylenediamine)；[Ru([9]aneS3)(en)(H2O)](2+)
• CAS: 875275-03-9
• 化学式: C₈H₂₂N₂ORuS₃
• 分子量: 359.543
• InChiKey: MHLLOMUTMGRETQ-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：

  ammonium hexafluorophosphate 、 [Ru(1,4,7-trithiacyclononane)(1,2-diaminoethane)(H2O)](2+) 、 [Ru(1,4,7-trithiacyclononane)(1,2-diaminoethane)Cl][PF₆] 、 水 在 silver nitrate 作用下， 以 甲醇 、 水 、 丙酮 为溶剂， 反应 48.0h， 以31%的产率得到[Ru(1,4,7-trithiacyclononane)(1,2-diaminoethane)(pyridine)][PF₆]₂
  参考文献：
  名称：

  Design of photoactivatable metallodrugs: Selective and rapid light-induced ligand dissociation from half-sandwich [Ru([9]aneS3)(N–N′)(py)]2+ complexes

  摘要：

  The synthesis of the inert Ru(II) half-sandwich coordination compounds, [Ru([9]aneS(3))(bpy)(py)][PF6](2) (1, [9]aneS(3) = 1,4,7-trithiacyclononane, bpy = 2,2'-bipyridine, py = pyridine), [Ru([9] aneS(3))(en)(py)][PF6](2) (2, en = 1,2-diaminoethane), and [Ru([9] aneN(3))(en)(dmso-S)][PF6](2) (3, [9] aneN(3) = 1,4,7-triazacyclo-nonane), is reported along with the X-ray crystal structure of 1. We investigated whether these complexes have photochemical properties which might make them suitable for use as pro-drugs in photochemotherapy. Complexes 1 and 2 underwent rapid (minutes) aquation with dissociation of the pyridine ligand in aqueous solution when irradiated with blue light (lambda = 420 or 467 nm). The photodecomposition of 3 was much slower. All complexes readily formed adducts with 9-ethylguanine (9-EtG) when this model nucleobase was present in the photolysis solution. Similarly, complex 1 formed adducts with the tripeptide glutathione (GSH), but only when photoactivated. HPLC and MS studies of 1 showed that irradiation promoted rapid formation of 1:1 (major) and 1:2 (minor) adducts of the oligonucleotide d(ATACATGCTACATA) with the fragment {Ru([9] aneS(3))(bpy)}(2+). Density functional theory (DFT) calculations and time-dependent DFT reproduced the major features of the absorption spectra and suggested that the lowest-lying triplet state with (MLCT)-M-3 character, which is readily accessible via intersystem crossing, might be responsible for the observed dissociative behavior of the excited states. These complexes are promising for further study as potential photochemotherapeutic agents. (C) 2012 Published by Elsevier B. V.

  DOI：

  10.1016/j.ica.2012.06.031
• 作为产物：
  描述：

  [Ru(1,4,7-trithiacyclononane)(dmso-S)₂Cl][PF₆] 在 silver nitrate 作用下， 以 甲醇 、 水 为溶剂， 反应 48.67h， 生成 [Ru(1,4,7-trithiacyclononane)(1,2-diaminoethane)(H2O)](2+)
  参考文献：
  名称：

  Design of photoactivatable metallodrugs: Selective and rapid light-induced ligand dissociation from half-sandwich [Ru([9]aneS3)(N–N′)(py)]2+ complexes

  摘要：

  The synthesis of the inert Ru(II) half-sandwich coordination compounds, [Ru([9]aneS(3))(bpy)(py)][PF6](2) (1, [9]aneS(3) = 1,4,7-trithiacyclononane, bpy = 2,2'-bipyridine, py = pyridine), [Ru([9] aneS(3))(en)(py)][PF6](2) (2, en = 1,2-diaminoethane), and [Ru([9] aneN(3))(en)(dmso-S)][PF6](2) (3, [9] aneN(3) = 1,4,7-triazacyclo-nonane), is reported along with the X-ray crystal structure of 1. We investigated whether these complexes have photochemical properties which might make them suitable for use as pro-drugs in photochemotherapy. Complexes 1 and 2 underwent rapid (minutes) aquation with dissociation of the pyridine ligand in aqueous solution when irradiated with blue light (lambda = 420 or 467 nm). The photodecomposition of 3 was much slower. All complexes readily formed adducts with 9-ethylguanine (9-EtG) when this model nucleobase was present in the photolysis solution. Similarly, complex 1 formed adducts with the tripeptide glutathione (GSH), but only when photoactivated. HPLC and MS studies of 1 showed that irradiation promoted rapid formation of 1:1 (major) and 1:2 (minor) adducts of the oligonucleotide d(ATACATGCTACATA) with the fragment {Ru([9] aneS(3))(bpy)}(2+). Density functional theory (DFT) calculations and time-dependent DFT reproduced the major features of the absorption spectra and suggested that the lowest-lying triplet state with (MLCT)-M-3 character, which is readily accessible via intersystem crossing, might be responsible for the observed dissociative behavior of the excited states. These complexes are promising for further study as potential photochemotherapeutic agents. (C) 2012 Published by Elsevier B. V.

  DOI：

  10.1016/j.ica.2012.06.031