Ru(2,2'-bipyridine)2(3-hydroxy-2-methyl-4H-thiopyran-4-thione(1-))PF6 | 1013397-34-6

• 英文名称: Ru(2,2'-bipyridine)2(3-hydroxy-2-methyl-4H-thiopyran-4-thione(1-))PF6
• 英文别名: Ru(bpy)2(ttma)PF6
• CAS: 1013397-34-6
• 化学式: C₂₆H₂₁N₄ORuS₂*F₆P
• 分子量: 715.645
• InChiKey: MBXAAAAJXRJMOQ-UHFFFAOYSA-M

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：

  Ru(2,2'-bipyridine)2(3-hydroxy-2-methyl-4H-thiopyran-4-thione(1-))PF6 在 2-iodoxybenzoic acid 作用下， 以 乙腈 为溶剂， 生成 Ru(2,2'-bipyridine)2(ttma-aldehyde)PF6*C5H12
  参考文献：
  名称：

  Unexpected C−H Activation of Ru(II)−Dithiomaltol Complexes upon Oxidation

  摘要：

  Thione-substituted derivatives of maltol are of interest in several applications of metal-based drugs. In order to investigate the effect of the oxygenation on such thione chelates, Ru complexes of 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol or Htma) and 3-hydroxy-2-methyl-4H-thiopyran-4-thione (dithiomaltol or Httma), [Ru(bPY)(2)(tma)](+), 1, and [Ru(bPY)(2)(ttma)](+), 2, were synthesized as diamagnetic PF6- salts. Peroxidation of 2 unexpectedly generated products of C-H activation at its pendant methyl group; an air-stable aldehyde [Ru(bPY)(2)(ttma-aldehyde)](+), 4, was the major product. In addition, an intermediate oxidation product [Ru(bPY)(2)(ttma-alcohol)](PF6), 3, was characterized. Both 3 and 4 are also formed by reaction of 2 with outersphere oxidants (e.g., Na2IrCl6) and by bulk electrolysis under anaerobic conditions. Similar oxidations of the analogous [Ru(bPY)(2)(ettma)](+), 2', complex (3-hydroxy-2-ethyl-4H-thiopyran-4-thione; ethyl dithiomaltol or Hettma) formed the corresponding ketone, [Ru(bPY)(2)(ettma-ketone)](PF6), 4', by oxidation at the same position adjacent to the conjugated ring. The structures of the aldehyde 4 and starting materials 1 and 2 have been confirmed by X-ray crystallography, and all complexes have been characterized by UV-vis, H-1 NMR, and IR spectroscopies. Initial mechanistic investigations are discussed.

  DOI：

  10.1021/ic7021962
• 作为产物：
  描述：

  顺-双(2,2'-二吡啶基)二氯化钌(II)二水合物 、 六氟磷酸钾 、 3-hydroxy-2-methyl-4H-thiopyran-4-thione 以 乙二醇 为溶剂， 以72%的产率得到Ru(2,2'-bipyridine)2(3-hydroxy-2-methyl-4H-thiopyran-4-thione(1-))PF6
  参考文献：
  名称：

  Unexpected C−H Activation of Ru(II)−Dithiomaltol Complexes upon Oxidation

  摘要：

  Thione-substituted derivatives of maltol are of interest in several applications of metal-based drugs. In order to investigate the effect of the oxygenation on such thione chelates, Ru complexes of 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol or Htma) and 3-hydroxy-2-methyl-4H-thiopyran-4-thione (dithiomaltol or Httma), [Ru(bPY)(2)(tma)](+), 1, and [Ru(bPY)(2)(ttma)](+), 2, were synthesized as diamagnetic PF6- salts. Peroxidation of 2 unexpectedly generated products of C-H activation at its pendant methyl group; an air-stable aldehyde [Ru(bPY)(2)(ttma-aldehyde)](+), 4, was the major product. In addition, an intermediate oxidation product [Ru(bPY)(2)(ttma-alcohol)](PF6), 3, was characterized. Both 3 and 4 are also formed by reaction of 2 with outersphere oxidants (e.g., Na2IrCl6) and by bulk electrolysis under anaerobic conditions. Similar oxidations of the analogous [Ru(bPY)(2)(ettma)](+), 2', complex (3-hydroxy-2-ethyl-4H-thiopyran-4-thione; ethyl dithiomaltol or Hettma) formed the corresponding ketone, [Ru(bPY)(2)(ettma-ketone)](PF6), 4', by oxidation at the same position adjacent to the conjugated ring. The structures of the aldehyde 4 and starting materials 1 and 2 have been confirmed by X-ray crystallography, and all complexes have been characterized by UV-vis, H-1 NMR, and IR spectroscopies. Initial mechanistic investigations are discussed.

  DOI：

  10.1021/ic7021962