[Os⁰(CO)(acetonitrile)(2,2′-bipyridine)]n | 799249-19-7

• 英文名称: [Os⁰(CO)(acetonitrile)(2,2′-bipyridine)]n
• 英文别名: [Os⁰(CO)(MeCN)(bpy)]n；[Os(0)(2,2'-bipyridine)(CO)(acetonitrile)]
• CAS: 799249-19-7
• 化学式: CO*C₂H₃N*C₁₀H₈N₂*Os
• 分子量: 415.45
• InChiKey: DWWUCCLHJLVDOE-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

• 作为产物：
  描述：

  [OsII(CO)(MeCN)(2,2′-bipyridine)Cl2] 以 乙腈 为溶剂， 生成 [Os⁰(CO)(acetonitrile)(2,2′-bipyridine)]n
  参考文献：
  名称：

  基于非桥接金属-金属键的氧化还原活性聚合物。[Os（bpy）（CO）（L）]（n）的电化学形成（bpy = 2,2'-联吡啶； L = CO，MeCN）及其还原形式：光谱电化学研究。

  摘要：

  应用可变温度和在不同溶剂中的IR，UV-vis和EPR光谱电化学技术，以原位研究具有非桥接Os-Os主链的电活性分子链的形成，特别是聚合物[Os（0）（bpy）（来自单核Os（II）羰基前体[Os（II）（bpy）（CO）（2）Cl（2）的CO）（2）]（n）（bpy = 2,2'-联吡啶）。单电子还原形式，[Os（II）（bpy（。）（-））（CO）（2）Cl（2）]（-）在低温下已进行了光谱表征。该自由基阴离子是电化学传播过程中负责金属-金属键形成的关键中间体。还获得了[[Os（0）（bpy（*）（-））（CO）（2）]（-）]（n）（CO（2）的富电子催化剂）的形成的明确光谱学证据。 ） 减少。聚合物种类在丁腈中的溶解度非常好，这对于它们在纳米科学中的潜在利用非常重要，例如作为分子导线。我们还表明，聚合物的单羰基乙腈衍生物[Os（0）（bpy）（CO）（MeCN）（2）Cl]（n）完全溶解。

  DOI：

  10.1021/ic049216i

文献信息

• Solvent-Dependent Formation of Os(0) Complexes by Electrochemical Reduction of [Os(CO)(2,2′-bipyridine)(L)Cl₂]; L = Cl^–, PrCN
  作者：Joanne Tory、Lisa King、Antonios Maroulis、Matti Haukka、Maria José Calhorda、František Hartl

  DOI：10.1021/ic402146t

  日期：2014.2.3

  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-.