Cp(CO)₂Mn{η²-HC≡CPh} | 12147-63-6

• 英文名称: Cp(CO)₂Mn{η²-HC≡CPh}
• CAS: 12147-63-6
• 化学式: C₁₅H₁₁MnO₂
• 分子量: 278.189
• InChiKey: PNICTAOCPMEIHA-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：

  bis(pentafluorophenyl)phosphinous acid 、 Cp(CO)₂Mn{η²-HC≡CPh} 以 乙醚 为溶剂， 反应 120.0h， 以71.1 mg的产率得到
  参考文献：
  名称：

  锰和R亚乙烯基配合物与氢磷酰基化合物的反应

  摘要：

  We studied the reactions of manganese and rhenium phenylvinylidenes Cp(CO)(2)M=C=C(H)Ph (Mn1 M = Mn; Re1 M = Re) with HP(O)R-2 (R = C6F5, Ph, and OEt) and HP(S)Ph-2, which resulted in the selective formation of eta(2)-E-phosphorylalkene complexes Cp(CO)(2)M{eta(2)-E-H[R-2(O)P]C=C(H)Ph} (Mn2, Re2 R = C6F5; Mn3, Re3 R = Ph; and Mn6, Re6 R = OEt) and Cp(CO)2M{eta(2)-E-H[Ph-2(S)P]C=C(H)Ph} (Mn5, Re5). The DFT/B3LYP(6-31G*) analysis showed the model reactions of Mn1 with HP(O)Me-2 and HP(O) (OMe)(2) to proceed via the initial transition state Cp(CO)(2){Ph(H)C=C=}Mn center dot center dot center dot HO-PR2 (TS1) where the minor PA form HO-PR2 is hydrogen-bonded to the metal, followed by stereoselective (trans- to the phenyl group) addition of the PA phosphorus atom to the C-alpha-vinylidene atom, which defines both the rate of the process and the anti-Markovnikov structure of the reaction product. The reactions can proceed at a relatively low content of the reactive PA form.

  DOI：

  10.1021/acs.organomet.6b00626
• 作为产物：
  描述：

  三羰基(η-环戊二烯基)合锰 、 苯乙炔 以 乙醚 为溶剂， 反应 1.0h， 以152.8 mg的产率得到Cp(CO)₂Mn{η²-HC≡CPh}
  参考文献：
  名称：

  锰和R亚乙烯基配合物与氢磷酰基化合物的反应

  摘要：

  We studied the reactions of manganese and rhenium phenylvinylidenes Cp(CO)(2)M=C=C(H)Ph (Mn1 M = Mn; Re1 M = Re) with HP(O)R-2 (R = C6F5, Ph, and OEt) and HP(S)Ph-2, which resulted in the selective formation of eta(2)-E-phosphorylalkene complexes Cp(CO)(2)M{eta(2)-E-H[R-2(O)P]C=C(H)Ph} (Mn2, Re2 R = C6F5; Mn3, Re3 R = Ph; and Mn6, Re6 R = OEt) and Cp(CO)2M{eta(2)-E-H[Ph-2(S)P]C=C(H)Ph} (Mn5, Re5). The DFT/B3LYP(6-31G*) analysis showed the model reactions of Mn1 with HP(O)Me-2 and HP(O) (OMe)(2) to proceed via the initial transition state Cp(CO)(2){Ph(H)C=C=}Mn center dot center dot center dot HO-PR2 (TS1) where the minor PA form HO-PR2 is hydrogen-bonded to the metal, followed by stereoselective (trans- to the phenyl group) addition of the PA phosphorus atom to the C-alpha-vinylidene atom, which defines both the rate of the process and the anti-Markovnikov structure of the reaction product. The reactions can proceed at a relatively low content of the reactive PA form.

  DOI：

  10.1021/acs.organomet.6b00626