Os(η(5)-C5H5)Cl(=C=CHPh)(PiPr3) | 196520-61-3

• 英文名称: Os(η(5)-C5H5)Cl(=C=CHPh)(PiPr3)
• 英文别名: OsCl(η5-C5H5)(=C=CHPh)(PiPr3)
• CAS: 196520-61-3
• 化学式: C₂₂H₃₂ClOsP
• 分子量: 553.123
• InChiKey: HLBXLAZLZDSZQO-UHFFFAOYSA-M

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：

  Os(η(5)-C5H5)Cl(=C=CHPh)(PiPr3) 、 甲基氯化镁 以 四氢呋喃 为溶剂， 以67%的产率得到[-OsH(η5-C5H5)(C(CH3)=CHC6H4-)(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
• 作为产物：
  描述：

  (η(5)-cyclopentadienyl)OsCl(triisopropylphosphine)2 、 苯乙炔 以 正戊烷 为溶剂， 以64%的产率得到Os(η(5)-C5H5)Cl(=C=CHPh)(PiPr3)
  参考文献：
  名称：

  迈尔络合物OsH 2 Cl 2（P i Pr 3）2作为制备新的环戊二烯基os化合物的前体

  摘要：

  的六配位配合物OSH 2氯2（P我镨3）2（1）反应以cyclopentadienylthallium给OS（η 5 -C 5 H ^ 5）氯（P我镨3）2（2）。在甲醇和丙酮中，2使氯配体解离，得到的金属片段能够活化三异丙基膦的甲基CH键，可以通过添加NaPF 6或TlPF 6将其分离为PF 6盐。。的1:10混合物的治疗2和NaBH 4在甲苯用1.0毫升甲醇，得到OSH（η的5 -C 5 H ^ 5）（P我镨3）2（4），其通过与HBF质子化4 ·OET 2产率[OSH 2（η 5 -C 5 H ^ 5）（P我镨3）2 ] BF 4（5）。在戊烷中，复杂的2种发生反应与亚磷酸三甲酯，得到OS（η 5 -C 5H 5）Cl {P（OMe）3 }（P i Pr 3）（6）。类似地，除了甲苯溶液甲基乙烯基酮和乙炔二的2产生一个膦配位体从位移2和Os的形成（η 5 -C 5 H ^ 5）氯{η

  DOI：

  10.1021/om970237c

文献信息

• Preparation and Characterization of a Monocyclopentadienyl Osmium−Allenylcarbene Complex
  作者：Miguel A. Esteruelas、Yohar A. Hernández、Ana M. López、Enrique Oñate

  DOI：10.1021/om700722e

  日期：2007.11.1

  The dihydride-dihydrogen complex [OsH2(eta(5)-C5H5)(eta(2)-H-2)((PPr3)-Pr-i)]BF4 (1) reacts with phenylacetylene to give the allenylcarbene derivative [Os(eta(5)-C5H5)=CPh(eta(2)-CH = C = CHPh)}((PPr3)-Pr-i)]BF4 (2) via the,pi-phenyl acetylene intermediate [Os(eta(5)-C5H5)(eta(2)-PhC CH)((PPr3)-Pr-i)]BF4 (3). The reactions of 2 with NaOMe and LiC CPh afford 3:1 mixtures of two hydride-osmaindene isomers of formula OsH(eta(5)-C5H5)C(C CPh)=CHC6H4}((PPr3)-Pr-i) (4 and 5) instead of the expected osmabenzyne complex.