[Os(η5-C5H5)(CH3CN)2(PiPr3)]BF4 | 876170-84-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: [Os(η5-C5H5)(CH3CN)2(PiPr3)]BF4
• 英文别名: acetonitrile;cyclopenta-1,3-diene;osmium(2+);tri(propan-2-yl)phosphane;tetrafluoroborate
• CAS: 876170-84-2
• 化学式: BF₄*C₁₈H₃₂N₂OsP
• 分子量: 584.444
• InChiKey: CXNSIRFCUGIXGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.46
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 [-OsH(η5-C5H5)(C(C6H5)=CHC6H4-)(PiPr3)] 、 乙腈 以 乙腈 为溶剂， 以77%的产率得到[Os(η5-C5H5)(CH3CN)2(PiPr3)]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