[1,5-bis(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II) | 171570-25-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环丁烷
• 英文名称: [1,5-bis(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II)
• CAS: 171570-25-5
• 化学式: C₁₀H₂₀N₂O₂PdS₂
• 分子量: 370.833
• InChiKey: YTNANJQOZKPDIL-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：

  [1,5-bis(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II) 以 甲醇 、 乙醚 为溶剂， 生成 [1,5-bis(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II) * 3 H2O
  参考文献：
  名称：

  Metallosulfoxides and -sulfones: Sulfur Oxygenates of [1,5-Bis(2-mercaptoethyl)-1,5-diazacyclooctanato]palladium(II)

  摘要：

  Successive sulfur-site oxygenation of the dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanato] palladium(II), Pd-1, using H2O2 as an O atom source produced all but one member of the series of palladium(II) complexes containing sulfinate (metallosulfone) and sulfenate (metallosulfoxide) S-donor ligands: the monosulfoxide, PdS(=O)R or Pd-4; bis(sulfoxide), Pd(S(=O)R)(2) or Pd-5; sulfone/sulfoxide, Pd(SO(2)R)S(=O)R or Pd-6; and the bis(sulfone) Pd(SO(2)R)(2) or Pd-3 complex. A unique site selectivity for the addition of a second O atom from H2O2 to thiolate sulfur of Pd-4 producing the bis(sulfoxide), Pd-5, exclusively, precluded the preparation of the monosulfone complex, Pd(SO(2)R)SR or Pd-2, via that route. However, the dithiolate Pd-1 reacts with O-2 photochemically in aprotic solvents, giving access to this last member of the series, Pd-2. Further reaction of Pd-2 with O-2 under UV photolysis gives the bis(sulfone) complex, Pd-3. The oxygenates were characterized by various spectroscopies, electrochemistry, and X-ray crystallography. Mass spectrometry delineated a single O atom loss pathway for the sulfoxide species, while SO2 and O-2 loss is found in sulfone cases. Electrochemical studies show that the addition of an O atom to a thiolate sulfur to create a sulfoxide S-donor results in a stabilization of the Pdl oxidation state in the range 50-70 mV, while the addition of an O atom to a sulfoxide sulfur to create a sulfone S-donor results in greater stabilization of the Pd-1 oxidation state in the range 190-220 mV. Complex Pd-2 crystallizes in the monoclinic P2(1)/c (No. 14) space group with a = 8.362(11) Angstrom, b = 12.102(9) Angstrom, c = 12.990(14) Angstrom, beta = 101.39(9)degrees, V = 1289(2) Angstrom(3) and Z = 4. Complex Pd-4 crystallizes in the orthorombic P2(1)2(1)2 space group with a 12.210(2) Angstrom, b = 15.931(4) Angstrom, c = 6.802(2) Angstrom, V = 1323.1(6) Angstrom(3), and Z = 4. Complex Pd-6 cocrystallizes with Pd-3 in the monoclinic C2/c space group with a 15.862(5) Angstrom, b = 8.146(2) Angstrom, c = 21.812(9) Angstrom, beta = 107.82(2)degrees, V = 2683(2) Angstrom(3), and Z = 8.

  DOI：

  10.1021/ic00129a012
• 作为产物：
  描述：

  [1-(mercaptoethyl)-5-(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II) 、 双氧水 以 甲醇 为溶剂， 以68%的产率得到[1,5-bis(sulfenatoethyl)-1,5-diazacyclooctanato]palladium(II)
  参考文献：
  名称：

  Metallosulfoxides and -sulfones: Sulfur Oxygenates of [1,5-Bis(2-mercaptoethyl)-1,5-diazacyclooctanato]palladium(II)

  摘要：

  Successive sulfur-site oxygenation of the dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanato] palladium(II), Pd-1, using H2O2 as an O atom source produced all but one member of the series of palladium(II) complexes containing sulfinate (metallosulfone) and sulfenate (metallosulfoxide) S-donor ligands: the monosulfoxide, PdS(=O)R or Pd-4; bis(sulfoxide), Pd(S(=O)R)(2) or Pd-5; sulfone/sulfoxide, Pd(SO(2)R)S(=O)R or Pd-6; and the bis(sulfone) Pd(SO(2)R)(2) or Pd-3 complex. A unique site selectivity for the addition of a second O atom from H2O2 to thiolate sulfur of Pd-4 producing the bis(sulfoxide), Pd-5, exclusively, precluded the preparation of the monosulfone complex, Pd(SO(2)R)SR or Pd-2, via that route. However, the dithiolate Pd-1 reacts with O-2 photochemically in aprotic solvents, giving access to this last member of the series, Pd-2. Further reaction of Pd-2 with O-2 under UV photolysis gives the bis(sulfone) complex, Pd-3. The oxygenates were characterized by various spectroscopies, electrochemistry, and X-ray crystallography. Mass spectrometry delineated a single O atom loss pathway for the sulfoxide species, while SO2 and O-2 loss is found in sulfone cases. Electrochemical studies show that the addition of an O atom to a thiolate sulfur to create a sulfoxide S-donor results in a stabilization of the Pdl oxidation state in the range 50-70 mV, while the addition of an O atom to a sulfoxide sulfur to create a sulfone S-donor results in greater stabilization of the Pd-1 oxidation state in the range 190-220 mV. Complex Pd-2 crystallizes in the monoclinic P2(1)/c (No. 14) space group with a = 8.362(11) Angstrom, b = 12.102(9) Angstrom, c = 12.990(14) Angstrom, beta = 101.39(9)degrees, V = 1289(2) Angstrom(3) and Z = 4. Complex Pd-4 crystallizes in the orthorombic P2(1)2(1)2 space group with a 12.210(2) Angstrom, b = 15.931(4) Angstrom, c = 6.802(2) Angstrom, V = 1323.1(6) Angstrom(3), and Z = 4. Complex Pd-6 cocrystallizes with Pd-3 in the monoclinic C2/c space group with a 15.862(5) Angstrom, b = 8.146(2) Angstrom, c = 21.812(9) Angstrom, beta = 107.82(2)degrees, V = 2683(2) Angstrom(3), and Z = 8.

  DOI：

  10.1021/ic00129a012