[Os(η⁶-p-cymene)(OH)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)](CF₃SO₃)

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [Os(η⁶-p-cymene)(OH)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)](CF₃SO₃)
• 英文别名: [Os(η⁶-p-cymene)(OH)IPr]OTf；[(η6-p-cymene)Os(OH)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)]OTf；1,3-bis[2,6-di(propan-2-yl)phenyl]-2H-imidazol-1-ium-2-ide;1-methyl-4-propan-2-ylbenzene;osmium(2+);trifluoromethanesulfonate;hydroxide
• 化学式: CF₃O₃S*C₃₇H₅₁N₂OOs
• 分子量: 879.095
• InChiKey: IOSVYXZXLCLZCY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  10.49
• 重原子数：
  49
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  73.1
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  甲醇 、 [Os(η⁶-p-cymene)(OH)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)](CF₃SO₃) 在 molecular sieves 4 Å 作用下， 以 甲醇 为溶剂， 以84%的产率得到[(η6-p-cymene)Os(OMe)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)]OTf
  参考文献：
  名称：

  Preparation, X-ray Structure, and Reactivity of an Osmium-Hydroxo Complex Stabilized by an N-Heterocyclic Carbene Ligand: A Base-Free Catalytic Precursor for Hydrogen Transfer from 2-Propanol to Aldehydes

  摘要：

  Complex [(eta(6)-p-cymene)OsCl(IPr)]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO3) reacts with NaOH to give [(eta(6)-p-cymene)Os(OH)(IPr)]OTf (2), which under hydrogen atmosphere affords [(eta(6)-p-cymene)OsH3(IPr)]OTf (3). The hydride ligands of 3 undergo exchange coupling, decreasing the H-H coupling constant from 206 to 74 Hz in the temperature range 213-178 K. Complex 3 is also obtained in a two-step procedure involving the reaction of 2 with NaBH4 to give (eta(6)-p-cymene)OsH2(IPr) (4) and the protonation of the latter with HOTf. Attempts to obtain 4 directly from 1 or (eta(6)-p-cymene)OSCl2(IPr) (5) are unsuccessful. In both reactions (eta(6)-p-cymene)OsHCl(IPr) (6) is formed. Complex 2 also reacts with methanol and 2-propanol. At -30 degrees C, the reaction with the first of them leads to [(eta(6)-p-cymene)Os(OMe)(IPr)]OTf (7), while with the second one, [(eta(6)-p-cymene)OsH{kappa(1)-OC(CH3)(2)}(IPr)]OTf (8) is obtained. Complex 2 is a catalyst precursor for the hydrogen transfer from 2-propanol to aldehydes, which does not need a base. The obtained TOF values are between 950 and 3500 h(-1). The X-ray structures of 2 and 6 are also reported.

  DOI：

  10.1021/om800183k
• 作为产物：
  描述：

  sodium hydroxide 、 [OsCl(η⁶-p-cymene)(IPr)]OTf 以 四氢呋喃 为溶剂， 以73%的产率得到[Os(η⁶-p-cymene)(OH)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)](CF₃SO₃)
  参考文献：
  名称：

  Preparation, X-ray Structure, and Reactivity of an Osmium-Hydroxo Complex Stabilized by an N-Heterocyclic Carbene Ligand: A Base-Free Catalytic Precursor for Hydrogen Transfer from 2-Propanol to Aldehydes

  摘要：

  Complex [(eta(6)-p-cymene)OsCl(IPr)]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO3) reacts with NaOH to give [(eta(6)-p-cymene)Os(OH)(IPr)]OTf (2), which under hydrogen atmosphere affords [(eta(6)-p-cymene)OsH3(IPr)]OTf (3). The hydride ligands of 3 undergo exchange coupling, decreasing the H-H coupling constant from 206 to 74 Hz in the temperature range 213-178 K. Complex 3 is also obtained in a two-step procedure involving the reaction of 2 with NaBH4 to give (eta(6)-p-cymene)OsH2(IPr) (4) and the protonation of the latter with HOTf. Attempts to obtain 4 directly from 1 or (eta(6)-p-cymene)OSCl2(IPr) (5) are unsuccessful. In both reactions (eta(6)-p-cymene)OsHCl(IPr) (6) is formed. Complex 2 also reacts with methanol and 2-propanol. At -30 degrees C, the reaction with the first of them leads to [(eta(6)-p-cymene)Os(OMe)(IPr)]OTf (7), while with the second one, [(eta(6)-p-cymene)OsH{kappa(1)-OC(CH3)(2)}(IPr)]OTf (8) is obtained. Complex 2 is a catalyst precursor for the hydrogen transfer from 2-propanol to aldehydes, which does not need a base. The obtained TOF values are between 950 and 3500 h(-1). The X-ray structures of 2 and 6 are also reported.

  DOI：

  10.1021/om800183k
• 作为试剂：
  描述：

  二苯乙腈 在 [Os(η⁶-p-cymene)(OH)(1,3-bis(2,6-diisopropylphenyl)imidazolylidene)](CF₃SO₃) 、 水 、 异丙醇 、 potassium hydroxide 作用下， 以 对二甲苯 为溶剂， 反应 9.0h， 以91%的产率得到2,2-联苯基乙酰胺
  参考文献：
  名称：

  Selective Hydration of Nitriles to Amides Promoted by an Os–NHC Catalyst: Formation and X-ray Characterization of κ²-Amidate Intermediates

  摘要：

  The complex [Os(eta(6)-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO3) reacts with benzonitrile and acetonitrile to afford the kappa(2)-amidate derivatives [Os(eta(6)-p-cymene){kappa O-2,N-NHC(O)-R}IPr]OTf (R = Ph (2), CH3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(eta(6)-benzene)-(OH)(CH3CN)IMe](+) (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the kappa(2)-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed.

  DOI：

  10.1021/om3006799