{(CO)5(η2-triphenylmethylallene)Mn}PF6 | 151078-33-0

• 英文名称: {(CO)5(η2-triphenylmethylallene)Mn}PF6
• CAS: 151078-33-0
• 化学式: C₂₇H₁₈MnO₅*F₆P
• 分子量: 622.339
• InChiKey: NDYBJBWMBJWWHN-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

• 作为反应物：
  描述：

  {(CO)5(η2-triphenylmethylallene)Mn}PF6 以 乙腈 为溶剂， 以27%的产率得到
  参考文献：
  名称：

  Annulation reaction of (triphenylmethyl)allene on a cationic metal complex and the reaction mechanism

  摘要：

  Treatment of CpW(CO)3CH2C=CH, 1a (Cp = eta5-C5H5), with Ph3CPF6 (Ph = C6H5) generates a cationic eta2-(triphenylmethyl)allene (tritylallene) complex [CpW(CO)3(eta2-CH2=C=CHCPh3)]PF6, 2a. When reacted with excess Me3NO, complex 2a liberates free tritylallene CH2=C=CHCPh3, 3. In acetonitrile, the tritylallene ligand of 2a undergoes an annulation reaction followed by decomplexation to give a mixture of 1,1-diphenyl-1,4-dihydronaphthalene, 4a, and 1,1-diphenyl-1,2-dihydronaphthalene, 4b. The first step of the cyclization is the intramolecular nucleophilic attack of the phenyl groups on the metal-coordinated allene moiety generating an arenium intermediate. Deprotonation of this intermediate by PPh3 affords a neutral metal-vinyl complex Cp(CO)3W[sigma-(C10H7)(C6H5)2], 7a, which has been isolated. Protonation of complex 7a with HBF4 gives 4a and 4b quantitatively. In the initial stage of this protonation, a pi-complex Cp(CO)3W[eta2-(C10H8)(C6H5)2]BF4, 9b, is observed and a fast workup enables isolation of 9b for spectroscopic characterization. Complex 9b gives 4b exclusively. The mechanism for the cyclization reaction is established by a spectroscopic characterization of 7a especially through 2D NMR techniques. The isomerization pathway that leads to 4b is established by protonation reaction of 7a using CF3COOD. Reactivity of such a cyclization reaction in a number of metal systems is rationalized by the electron donor/acceptor ability of the metal fragment.

  DOI：

  10.1021/om00034a032
• 作为产物：
  描述：

  、 tritylium hexafluorophosphate 以 二氯甲烷 为溶剂， 生成 {(CO)5(η2-triphenylmethylallene)Mn}PF6
  参考文献：
  名称：

  Annulation reaction of (triphenylmethyl)allene on a cationic metal complex and the reaction mechanism

  摘要：

  Treatment of CpW(CO)3CH2C=CH, 1a (Cp = eta5-C5H5), with Ph3CPF6 (Ph = C6H5) generates a cationic eta2-(triphenylmethyl)allene (tritylallene) complex [CpW(CO)3(eta2-CH2=C=CHCPh3)]PF6, 2a. When reacted with excess Me3NO, complex 2a liberates free tritylallene CH2=C=CHCPh3, 3. In acetonitrile, the tritylallene ligand of 2a undergoes an annulation reaction followed by decomplexation to give a mixture of 1,1-diphenyl-1,4-dihydronaphthalene, 4a, and 1,1-diphenyl-1,2-dihydronaphthalene, 4b. The first step of the cyclization is the intramolecular nucleophilic attack of the phenyl groups on the metal-coordinated allene moiety generating an arenium intermediate. Deprotonation of this intermediate by PPh3 affords a neutral metal-vinyl complex Cp(CO)3W[sigma-(C10H7)(C6H5)2], 7a, which has been isolated. Protonation of complex 7a with HBF4 gives 4a and 4b quantitatively. In the initial stage of this protonation, a pi-complex Cp(CO)3W[eta2-(C10H8)(C6H5)2]BF4, 9b, is observed and a fast workup enables isolation of 9b for spectroscopic characterization. Complex 9b gives 4b exclusively. The mechanism for the cyclization reaction is established by a spectroscopic characterization of 7a especially through 2D NMR techniques. The isomerization pathway that leads to 4b is established by protonation reaction of 7a using CF3COOD. Reactivity of such a cyclization reaction in a number of metal systems is rationalized by the electron donor/acceptor ability of the metal fragment.

  DOI：

  10.1021/om00034a032