[Ru(η3-CH2CHCMe2)Cl(CO)(PPh3)2] | 780790-19-4

• 英文名称: [Ru(η3-CH2CHCMe2)Cl(CO)(PPh3)2]
• CAS: 780790-19-4
• 化学式: C₄₂H₃₉ClOP₂Ru
• 分子量: 758.242
• InChiKey: NRKJMJTYFZSSHY-UHFFFAOYSA-M

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：

  [Ru(η3-CH2CHCMe2)Cl(CO)(PPh3)2] 以 二氯甲烷 为溶剂， 以41%的产率得到[Ru(η3-CH2CMeCHMe)Cl(CO)(PPh3)2]
  参考文献：
  名称：

  Isomerism of [Ru(η³-allyl)Cl(CO)(PPh₃)₂]

  摘要：

  Treatment of [RuHCl(CO)(PPh3)(3)] with CH2=C=CMe2 produced the new allyl complex [Ru(eta(3)-CH2CHCMe2)Cl(CO)(PPh3)(2)], which slowly isomerizes to [Ru(eta(3)-CH2CMeCHMe)Cl(CO)(PPh3)(2)], in both solution and the solid state. While both endo and exo isomers can be observed by solution NMR for the allyl complex [Ru(eta(3)-CH2CHCMe2)Cl(CO)(PPh3)(2)], only the endo isomer was detected for other related analogous allyl complexes [Ru(eta(3)-allyl)Cl(CO)(PPh3)(2)] (e.g. allyl = CH2CMeCHMe, CH2CHCHPh). The isomeric behavior has been investigated by computational chemistry. The theoretical calculations show that the metal-eta(3)-allyl interaction in an endo isomer of [Ru(eta(3)-allyl)Cl(CO)(PR3)(2)] complexes is stronger than that in an exo isomer, because the structural arrangement provides an optimal situation to maximize the Ru(d)-to-CO(pi*) back-bonding interaction. However, substituents at the eta(3)-allyl ligand also play an important role in determining the relative stability. It was found that an anti substituent (with respect to the central allylic substituent) at one of the terminal carbons destabilizes the endo isomer more significantly and therefore makes the endo and exo isomers comparable in terms of their relative stabilities. A syn substituent at one of the terminal carbons is, however, found to have a negligible effect on the relative stability. The endo-exo interconversion was found to proceed by intervention of eta(1)-allyl intermediates instead of a direct eta(3)-allyl rotation.

  DOI：

  10.1021/om049646g
• 作为产物：
  描述：

  [RuHCl(CO)(PPh₃)₃] 、 3-甲基-1,2-丁二烯 以 二氯甲烷 为溶剂， 以84%的产率得到[Ru(η3-CH2CHCMe2)Cl(CO)(PPh3)2]
  参考文献：
  名称：

  Isomerism of [Ru(η³-allyl)Cl(CO)(PPh₃)₂]

  摘要：

  Treatment of [RuHCl(CO)(PPh3)(3)] with CH2=C=CMe2 produced the new allyl complex [Ru(eta(3)-CH2CHCMe2)Cl(CO)(PPh3)(2)], which slowly isomerizes to [Ru(eta(3)-CH2CMeCHMe)Cl(CO)(PPh3)(2)], in both solution and the solid state. While both endo and exo isomers can be observed by solution NMR for the allyl complex [Ru(eta(3)-CH2CHCMe2)Cl(CO)(PPh3)(2)], only the endo isomer was detected for other related analogous allyl complexes [Ru(eta(3)-allyl)Cl(CO)(PPh3)(2)] (e.g. allyl = CH2CMeCHMe, CH2CHCHPh). The isomeric behavior has been investigated by computational chemistry. The theoretical calculations show that the metal-eta(3)-allyl interaction in an endo isomer of [Ru(eta(3)-allyl)Cl(CO)(PR3)(2)] complexes is stronger than that in an exo isomer, because the structural arrangement provides an optimal situation to maximize the Ru(d)-to-CO(pi*) back-bonding interaction. However, substituents at the eta(3)-allyl ligand also play an important role in determining the relative stability. It was found that an anti substituent (with respect to the central allylic substituent) at one of the terminal carbons destabilizes the endo isomer more significantly and therefore makes the endo and exo isomers comparable in terms of their relative stabilities. A syn substituent at one of the terminal carbons is, however, found to have a negligible effect on the relative stability. The endo-exo interconversion was found to proceed by intervention of eta(1)-allyl intermediates instead of a direct eta(3)-allyl rotation.

  DOI：

  10.1021/om049646g