[(C5Me5)Ru(triphenylphosphine)2(vinylidene)][PF6] | 187530-08-1

• 英文名称: [(C5Me5)Ru(triphenylphosphine)2(vinylidene)][PF6]
• CAS: 187530-08-1
• 化学式: C₄₈H₄₇P₂Ru*F₆P
• 分子量: 931.883
• InChiKey: UIIFQNPZDJNLKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(C5Me5)Ru(triphenylphosphine)2(vinylidene)][PF6] 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以77%的产率得到[Ru(η5-C5Me5)(PPh3)2(-C≡CH)]
  参考文献：
  名称：

  Ethinylkomplexe des Rutheniums mit terminalen Hauptgruppenelement-Substituenten: Systematischer Aufbau metallgebundener Phosphoniumacetylid-Liganden R′R2P(+)-C≡C|(−)

  摘要：

  Treatment of Cp* RuL2Cl (Cp* = C5Me5; L = PPh3, PMe3) with Me3SiC=C:H in the presence of NH4[PF6] in CH2Cl2 yielded the expected vinylidene compounds [Cp *RuL2=C=CH2][PF6] with L = PPh3 (1) and PMe3 (1a), which were deprotonated by KOBut in THF to give the corresponding ethynyl complexes Cp*Ru(PPh3)(2)C=CH (2) and Cp*Ru(PMe3)(2)C=CH (2a). Metalation of 2 using n-BuLi or t-BuLi in THF-hexane, followed by reaction of the lithio intermediate Cp*Ru(PPh3)(2)C=CLi with CIER3 (E = Si, Ge, Sn) or ClPR2, resulted in the formation of substituted derivatives, Cp*Ru(PPh3)(2)C=CER3 [ER3 = SiMe3 (3), GeMe3 (4), SnBu3n (5)] and Cp*Ru(PPh3)(2)C=CPR2 [PR2 = PPh2 (6), PBu2t (7)] respectively. Quaternization of 6 and 7 by alkyl iodides in toluene smoothly produced phosphonioethynyl complexes, [Cp*Ru(PPh3)(2)C=CPR2R']I [PR2R' = PPh2Me (8), (PBu2Me)-Me-t (9), PPh2Prn (10), (PBu2Prn)-Pr-t(11)], the cations of which may be regarded as donor/acceptor-stabilized derivatives of dicarbon, C-2.

  DOI：

  10.1016/s0022-328x(97)00005-3
• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 五甲基环戊二烯基双(三苯基膦)氯化钌(II) 、 三甲基乙炔基硅 以 二氯甲烷 为溶剂， 以73%的产率得到[(C5Me5)Ru(triphenylphosphine)2(vinylidene)][PF6]
  参考文献：
  名称：

  Ethinylkomplexe des Rutheniums mit terminalen Hauptgruppenelement-Substituenten: Systematischer Aufbau metallgebundener Phosphoniumacetylid-Liganden R′R2P(+)-C≡C|(−)

  摘要：

  Treatment of Cp* RuL2Cl (Cp* = C5Me5; L = PPh3, PMe3) with Me3SiC=C:H in the presence of NH4[PF6] in CH2Cl2 yielded the expected vinylidene compounds [Cp *RuL2=C=CH2][PF6] with L = PPh3 (1) and PMe3 (1a), which were deprotonated by KOBut in THF to give the corresponding ethynyl complexes Cp*Ru(PPh3)(2)C=CH (2) and Cp*Ru(PMe3)(2)C=CH (2a). Metalation of 2 using n-BuLi or t-BuLi in THF-hexane, followed by reaction of the lithio intermediate Cp*Ru(PPh3)(2)C=CLi with CIER3 (E = Si, Ge, Sn) or ClPR2, resulted in the formation of substituted derivatives, Cp*Ru(PPh3)(2)C=CER3 [ER3 = SiMe3 (3), GeMe3 (4), SnBu3n (5)] and Cp*Ru(PPh3)(2)C=CPR2 [PR2 = PPh2 (6), PBu2t (7)] respectively. Quaternization of 6 and 7 by alkyl iodides in toluene smoothly produced phosphonioethynyl complexes, [Cp*Ru(PPh3)(2)C=CPR2R']I [PR2R' = PPh2Me (8), (PBu2Me)-Me-t (9), PPh2Prn (10), (PBu2Prn)-Pr-t(11)], the cations of which may be regarded as donor/acceptor-stabilized derivatives of dicarbon, C-2.

  DOI：

  10.1016/s0022-328x(97)00005-3

文献信息

• Unexpected Formation of the Vinyl−Phosphonio Complex [CpRu(PPh₃)(C₆H₄PPh₂CHCH₂)][PF₆] from a Vinylidene Complex via Nucleophilic Addition and Ortho Metalation of Triphenylphosphine
  作者：Kiyotaka Onitsuka、Masayoshi Nishii、Yuji Matsushima、Shigetoshi Takahashi

  DOI：10.1021/om049440f

  日期：2004.11.1

  results obtained by using a deuterium-labeled complex and a methyldiphenylphosphine analogue indicated that the present reaction proceeded via nucleophilic addition to the α-carbon of the vinylidene group, followed by ortho metalation of the phenyl ring on the cationic phosphorus atom.

  Ru-亚乙烯基配合物与三苯基膦的反应导致乙烯基-膦酰基配合物的形成，收率很高。通过使用氘标记的配合物和甲基二苯基膦类似物获得的结果表明，本反应通过向亚乙烯基的α-碳上亲核加成，然后在阳离子磷原子上对苯环进行邻位金属化而进行。