[Os(η5-C5H5)(η3-CH2CHCHPh)(PiPr3)] | 876170-75-1

• 英文名称: [Os(η5-C5H5)(η3-CH2CHCHPh)(PiPr3)]
• CAS: 876170-75-1
• 化学式: C₂₃H₃₅OsP
• 分子量: 532.705
• InChiKey: BKQSDCNCCIXNEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  四氟硼酸-二乙醚络合物 、 [Os(η5-C5H5)(η3-CH2CHCHPh)(PiPr3)] 以 乙醚 为溶剂， 以82%的产率得到[OsH(η5-C5H5)(η3-CH2CHCHPh)(P(i)Pr3)]BF4
  参考文献：
  名称：

  Preparation of Half-Sandwich Osmium-Allyl Complexes by Consecutive C−C Bond Formation and C−H Bond Activation Reactions

  摘要：

  The vinylidene complex OsH(eta(5)-C5H5)Cl(CH3)(=C=CHPh)((PPr3)-Pr-i) (1) reacts with MgCI to give the osmaindene OsH(eta-5-C5H5){C(CH3)=CHC6H4}(PiPr3) (2), which isomerizes into the exo-allyl compound Os(eta(5) -C5H5)(eta(5)- C5H5)(eta(CH2CHPh)-C-3)(PiPr3) (3) in refluxing toluene. Treatment of 3 with HBF4 center dot OEt2 leads to the endo-&-allyl derivative [OsH(eta(5)-C5H5)eta(3)-CH2CHCHPh}((PPr3)-Pr-i)]BF4 (4), which can be also obtained by addition of HBF4 center dot OEt2 to 2. Complex 4 contains the terminal CHPh group of the ally] cisoid disposed to the phosphine. In dichloromethane at 40 degrees C, it isomerizes into an endo-allyl isomer 5 with the terminal CHPh group cisoid disposed to the hydride. Complex 1 also reacts with EtMgCl. The reaction affordsOsH(eta(5) -C5C5){C(CH2CH3)=CHC6H4}((PPr3)-Pr-i) (6), which in toluene at 70 degrees C is converted into the exoallyl complex Os(eta(5)-C5H5)eta(3)-CH(CH3)CHCHPhl(P(i)Pr3) (7). Treatment of 7 with HBF4 center dot OEt2 leads to an equilibrium mixture of exo-d(4)-allyl derivatives of formula [OsH(eta(5) -C5H5)eta(3)-CH(CH3)CHCHPh}(PiPr(3))]BF4 (8 and 9). The addition of HBF4 center dot OEt2 to 6 gives an endo-&-allyl isomer, 10, which is transformed into the equilibrium mixture of 8 and 9 after 7 days in dichloromethane at 40 degrees C. Treatment of 1withPhMgCI gives rise to OsH(eta(5)-C5H5){C(Ph)=CHC6H4}((PPr3)-Pr-i) (11), which reacts with HBF4 center dot Et-2, in the presence of acetonitrile to afford stilbene and the solvento complex [Os(eta(5)-C5H5)(CH3CN)(2)((PPr3)-Pr-i)]BF4 (12). The X-ray structures of 3, 5, and 8 are also reported.

  DOI：

  10.1021/om050907b
• 作为产物：
  描述：

  [-OsH(η5-C5H5)(C(CH3)=CHC6H4-)(PiPr3)] 以 甲苯 为溶剂， 以83%的产率得到[Os(η5-C5H5)(η3-CH2CHCHPh)(PiPr3)]
  参考文献：
  名称：

  Preparation of Half-Sandwich Osmium-Allyl Complexes by Consecutive C−C Bond Formation and C−H Bond Activation Reactions

  摘要：

  The vinylidene complex OsH(eta(5)-C5H5)Cl(CH3)(=C=CHPh)((PPr3)-Pr-i) (1) reacts with MgCI to give the osmaindene OsH(eta-5-C5H5){C(CH3)=CHC6H4}(PiPr3) (2), which isomerizes into the exo-allyl compound Os(eta(5) -C5H5)(eta(5)- C5H5)(eta(CH2CHPh)-C-3)(PiPr3) (3) in refluxing toluene. Treatment of 3 with HBF4 center dot OEt2 leads to the endo-&-allyl derivative [OsH(eta(5)-C5H5)eta(3)-CH2CHCHPh}((PPr3)-Pr-i)]BF4 (4), which can be also obtained by addition of HBF4 center dot OEt2 to 2. Complex 4 contains the terminal CHPh group of the ally] cisoid disposed to the phosphine. In dichloromethane at 40 degrees C, it isomerizes into an endo-allyl isomer 5 with the terminal CHPh group cisoid disposed to the hydride. Complex 1 also reacts with EtMgCl. The reaction affordsOsH(eta(5) -C5C5){C(CH2CH3)=CHC6H4}((PPr3)-Pr-i) (6), which in toluene at 70 degrees C is converted into the exoallyl complex Os(eta(5)-C5H5)eta(3)-CH(CH3)CHCHPhl(P(i)Pr3) (7). Treatment of 7 with HBF4 center dot OEt2 leads to an equilibrium mixture of exo-d(4)-allyl derivatives of formula [OsH(eta(5) -C5H5)eta(3)-CH(CH3)CHCHPh}(PiPr(3))]BF4 (8 and 9). The addition of HBF4 center dot OEt2 to 6 gives an endo-&-allyl isomer, 10, which is transformed into the equilibrium mixture of 8 and 9 after 7 days in dichloromethane at 40 degrees C. Treatment of 1withPhMgCI gives rise to OsH(eta(5)-C5H5){C(Ph)=CHC6H4}((PPr3)-Pr-i) (11), which reacts with HBF4 center dot Et-2, in the presence of acetonitrile to afford stilbene and the solvento complex [Os(eta(5)-C5H5)(CH3CN)(2)((PPr3)-Pr-i)]BF4 (12). The X-ray structures of 3, 5, and 8 are also reported.

  DOI：

  10.1021/om050907b