mer-[Os(bpy)Cl3(CH3OH)]*CH3OH | 1539274-41-3

• 英文名称: mer-[Os(bpy)Cl3(CH3OH)]*CH3OH
• CAS: 1539274-41-3
• 化学式: CH₄O*C₁₁H₁₂Cl₃N₂OOs
• 分子量: 516.83
• InChiKey: UUXMLDFAIXKQOF-UHFFFAOYSA-K

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：

  一氧化碳 、 mer-[Os(bpy)Cl3(CH3OH)]*CH3OH 以 二氯甲烷 为溶剂， 60.0 ℃ 、5.0 MPa 条件下， 反应 18.0h， 以69%的产率得到mer-[Os(CO)(2,2′-bipyridine)Cl3]
  参考文献：
  名称：

  Solvent-Dependent Formation of Os(0) Complexes by Electrochemical Reduction of [Os(CO)(2,2′-bipyridine)(L)Cl₂]; L = Cl^–, PrCN

  摘要：

  Cyclic voltammetry and ultraviolet-visible/infrared (UV-vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer[Os-III(CO) (bpy)Cl-3] (bpy = 2,2'-bipyridine) and trans(Cl)- [Os-II(CO) (PrCN)(bpy)Cl-2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[Os-II(CO) (bpy(center dot-))Cl-3](2-) and trans(Cl)-[Os-II(CO)(PrCN) (bpy(center dot-))Cl-2](-), respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[Os-III(CO) (bpy)Cl-3] is reduced in THF to give ultimately an Os-Os-bonded polymer, probably [Os-0(CO) (THF)(bpy)], whereas in PrCN the well-soluble, probably mononuclear [Os (CO) (PrCN)(bpy)], species is formed. The same products were observed for the 2 electron reduction of trans(Cl)-[Os-II(CO)(PrCN) (bpy)Cl-2] in both solvents. In MeCN, similar to THF, the [Os-0(CO) (MeCN)(bpy)],, polymer is produced. It is noteworthy that the bpy ligand in mononuclear [Os-0(CO) (PrCN)(bpy)] is reduced to the corresponding radical anion at a significantly less negative potential than it is in polymeric [Os-0(CO) (THF)(bpy)](n) : Delta E-1/2 = 0.67 V. Major differences also exist in the IR spectra of the Os(0) species: the polymer shows a broad v(CO) band at much smaller wavenumbers compared to the soluble Os(0) monomer that exhibits a characteristic v(Pr-CN) band below 2200 cm(-1) in addition to the intense and narrow v(CO) absorption band. For the first time, in this work the M-0-bpy (M = Ru, Os) mono- and dicarbonyl species soluble in PrCN have been formulated as a mononuclear complex. Density functional theory (DFT) and time-dependent-DFT calculations confirm the Os(0) oxidation state and suggest that [Os-0(CO) (PrCN)(bpy)] is a square planar moiety. The reversible bpy-based reduction of [Os-0(CO) (PrCN)(bpy)] triggers catalytic reduction of CO2 to CO and HCOO-.

  DOI：

  10.1021/ic402146t
• 作为产物：
  描述：

  甲醇 、 2,2'-联吡啶 、 osmium tri chloride trihydrate 在 氢气 作用下， 反应 24.0h， 以40%的产率得到mer-[Os(bpy)Cl3(CH3OH)]*CH3OH
  参考文献：
  名称：

  Solvent-Dependent Formation of Os(0) Complexes by Electrochemical Reduction of [Os(CO)(2,2′-bipyridine)(L)Cl₂]; L = Cl^–, PrCN

  摘要：

  Cyclic voltammetry and ultraviolet-visible/infrared (UV-vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer[Os-III(CO) (bpy)Cl-3] (bpy = 2,2'-bipyridine) and trans(Cl)- [Os-II(CO) (PrCN)(bpy)Cl-2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[Os-II(CO) (bpy(center dot-))Cl-3](2-) and trans(Cl)-[Os-II(CO)(PrCN) (bpy(center dot-))Cl-2](-), respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[Os-III(CO) (bpy)Cl-3] is reduced in THF to give ultimately an Os-Os-bonded polymer, probably [Os-0(CO) (THF)(bpy)], whereas in PrCN the well-soluble, probably mononuclear [Os (CO) (PrCN)(bpy)], species is formed. The same products were observed for the 2 electron reduction of trans(Cl)-[Os-II(CO)(PrCN) (bpy)Cl-2] in both solvents. In MeCN, similar to THF, the [Os-0(CO) (MeCN)(bpy)],, polymer is produced. It is noteworthy that the bpy ligand in mononuclear [Os-0(CO) (PrCN)(bpy)] is reduced to the corresponding radical anion at a significantly less negative potential than it is in polymeric [Os-0(CO) (THF)(bpy)](n) : Delta E-1/2 = 0.67 V. Major differences also exist in the IR spectra of the Os(0) species: the polymer shows a broad v(CO) band at much smaller wavenumbers compared to the soluble Os(0) monomer that exhibits a characteristic v(Pr-CN) band below 2200 cm(-1) in addition to the intense and narrow v(CO) absorption band. For the first time, in this work the M-0-bpy (M = Ru, Os) mono- and dicarbonyl species soluble in PrCN have been formulated as a mononuclear complex. Density functional theory (DFT) and time-dependent-DFT calculations confirm the Os(0) oxidation state and suggest that [Os-0(CO) (PrCN)(bpy)] is a square planar moiety. The reversible bpy-based reduction of [Os-0(CO) (PrCN)(bpy)] triggers catalytic reduction of CO2 to CO and HCOO-.

  DOI：

  10.1021/ic402146t