[(η6-p-cymene)RuCl(=C=C=CMePh)(PCy3)][OTf] | 885024-55-5

• 英文名称: [(η6-p-cymene)RuCl(=C=C=CMePh)(PCy3)][OTf]
• CAS: 885024-55-5
• 化学式: CF₃O₃S*C₃₈H₅₅ClPRu
• 分子量: 828.422
• InChiKey: ZGULRCZGYPHSHU-UHFFFAOYSA-L

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：
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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：

  [(η6-p-cymene)RuCl(=C=C=CMePh)(PCy3)][OTf] 、 三氟甲磺酸 以 二氯甲烷-D2 为溶剂， 生成 [(η6-p-cymene)RuCl(.ident.C-CH=CMePh)(PCy3)][OTf]2
  参考文献：
  名称：

  Allenylidene-to-Indenylidene Rearrangement in Arene−Ruthenium Complexes: A Key Step to Highly Active Catalysts for Olefin Metathesis Reactions

  摘要：

  The allenyliclene-ruthenium complexes [(eta(6)-arene)RuCl(=C=C=CR2)(PR'(3))]OTf (R-2 = Ph; fluorene, Ph, Me; PR'3 = PCY3, (PPr3)-Pr-i, PPh3) (OTf = CF3SO3) on protonation with HOTf at -40 degrees C are completely transformed into alkenylcarbyne complexes [(eta(6)-p-cymene)RuCl( CCH=CR2)(PR3)](OTf)(2). At -20 degrees C the latter undergo intramolecular rearrangement of the allenylidene ligand, with release of HOTf, into the indenylidene group in derivatives [(eta(6)-arene)RuCl(indenylidene)(PR3)]OTf. The in situ-prepared indenylidene- ruthenium complexes are efficient catalyst precursors for ring-opening metathesis polymerization of cyclooctene and cyclopentene, reaching turnover frequencies of nearly 300 s(-1) at room temperature. Isolation of these derivatives improves catalytic activity for the ring-closing metathesis of a variety of dienes and enynes. A mechanism based on the initial release of arene ligand and the in situ generation of the active catalytic species RuCI(OTf)(=CH2)(PR3) is proposed.

  DOI：

  10.1021/ja0579762
• 作为产物：
  描述：

  2-苯基-3-丁炔-2-醇 、 [RuCl(PCy3)(p-cymene)]OTf 以 二氯甲烷 为溶剂， 生成 [(η6-p-cymene)RuCl(=C=C=CMePh)(PCy3)][OTf]
  参考文献：
  名称：

  Allenylidene-to-Indenylidene Rearrangement in Arene−Ruthenium Complexes: A Key Step to Highly Active Catalysts for Olefin Metathesis Reactions

  摘要：

  The allenyliclene-ruthenium complexes [(eta(6)-arene)RuCl(=C=C=CR2)(PR'(3))]OTf (R-2 = Ph; fluorene, Ph, Me; PR'3 = PCY3, (PPr3)-Pr-i, PPh3) (OTf = CF3SO3) on protonation with HOTf at -40 degrees C are completely transformed into alkenylcarbyne complexes [(eta(6)-p-cymene)RuCl( CCH=CR2)(PR3)](OTf)(2). At -20 degrees C the latter undergo intramolecular rearrangement of the allenylidene ligand, with release of HOTf, into the indenylidene group in derivatives [(eta(6)-arene)RuCl(indenylidene)(PR3)]OTf. The in situ-prepared indenylidene- ruthenium complexes are efficient catalyst precursors for ring-opening metathesis polymerization of cyclooctene and cyclopentene, reaching turnover frequencies of nearly 300 s(-1) at room temperature. Isolation of these derivatives improves catalytic activity for the ring-closing metathesis of a variety of dienes and enynes. A mechanism based on the initial release of arene ligand and the in situ generation of the active catalytic species RuCI(OTf)(=CH2)(PR3) is proposed.

  DOI：

  10.1021/ja0579762