cis,cis-dichloro(bis(2-(diisopropylphosphino)ethyl) ether)(dihydrogen)ruthenium | 852995-11-0

• 英文名称: cis,cis-dichloro(bis(2-(diisopropylphosphino)ethyl) ether)(dihydrogen)ruthenium
• CAS: 852995-11-0；853062-76-7
• 化学式: C₁₆H₃₈Cl₂OP₂Ru
• 分子量: 480.401
• InChiKey: JWHPPCVQFGUKBM-UHFFFAOYSA-L

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：

  cis,cis-dichloro(bis(2-(diisopropylphosphino)ethyl) ether)(dihydrogen)ruthenium 、 氘 以 氘代苯 为溶剂， 生成 cis,cis-dichloro(bis(2-(diisopropylphosphino)ethyl) ether)(D2)ruthenium
  参考文献：
  名称：

  Substituents Effects in POP Pincer Complexes of Ruthenium

  摘要：

  Reactions of [RuCl2(p-cymene)](2) with ((Bu2PCH2CH2)-Bu-t)(2)O (POP-Bu-t) and (Pr2PCH2CH2)(2)O (POP-Pr-i) afforded RuCl2(POP-Bu-t) (1) and [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)]Cl (2 center dot Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a gamma-agostic C-H center dot center dot center dot Ru interaction of one Bu-t group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N-2)Cl(POP-Bu-t)]BPh4 (4), which also showed agostic bonding of a Bu-t group, was obtained by substitution of N-2 for Cl- in 1, in the presence of NaBPh4. Compound 2 center dot Cl readily underwent ion exchange with LiBPh4 or LiPF6 to give 2 center dot BPh4 or 2 center dot PF6 salts, respectively. A crystallographic analysis of 2 center dot PF6 established a co-facial bioctahedral geometry of the [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)](+) cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H-2 afforded the dihydrogen complexes cis,trans-Ru(H-2)Cl-2(POP-Bu-t) (3) and cis,cis-Ru(H-2)Cl-2(POP-Pr-i) (5), respectively. The H-H bond distances are very similar in both compounds, r(H-H) = 1.0 +/- 0.1 angstrom, based on the T-1min and J(HD) data and results of DFT calculations. Reaction of 2 with N-2 gave the dinitrogen complex cis,cis-Ru(N-2)Cl-2(POP-Pr-i) (6), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP-Bu-t and POP-iPr complexes 1-6.

  DOI：

  10.1021/om050053v
• 作为产物：
  描述：

  cis,cis-dichloro(bis(2-(diisopropylphosphino)ethyl) ether)(η1-dinitrogen)ruthenium 、 氢气 以 苯 为溶剂， 生成 cis,cis-dichloro(bis(2-(diisopropylphosphino)ethyl) ether)(dihydrogen)ruthenium
  参考文献：
  名称：

  Substituents Effects in POP Pincer Complexes of Ruthenium

  摘要：

  Reactions of [RuCl2(p-cymene)](2) with ((Bu2PCH2CH2)-Bu-t)(2)O (POP-Bu-t) and (Pr2PCH2CH2)(2)O (POP-Pr-i) afforded RuCl2(POP-Bu-t) (1) and [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)]Cl (2 center dot Cl), respectively. The POP ligand is coordinated in a mer fashion in complex 1, whose crystal structure revealed a gamma-agostic C-H center dot center dot center dot Ru interaction of one Bu-t group. Spectroscopic evidence indicated that this agostic interaction is retained in 1 in solution. A related compound, [Ru(N-2)Cl(POP-Bu-t)]BPh4 (4), which also showed agostic bonding of a Bu-t group, was obtained by substitution of N-2 for Cl- in 1, in the presence of NaBPh4. Compound 2 center dot Cl readily underwent ion exchange with LiBPh4 or LiPF6 to give 2 center dot BPh4 or 2 center dot PF6 salts, respectively. A crystallographic analysis of 2 center dot PF6 established a co-facial bioctahedral geometry of the [Ru-2(mu-Cl)(3)(POP-Pr-i)(2)](+) cation containing two POP ligands coordinated in a fac fashion. Reactions of 1 and 2 with H-2 afforded the dihydrogen complexes cis,trans-Ru(H-2)Cl-2(POP-Bu-t) (3) and cis,cis-Ru(H-2)Cl-2(POP-Pr-i) (5), respectively. The H-H bond distances are very similar in both compounds, r(H-H) = 1.0 +/- 0.1 angstrom, based on the T-1min and J(HD) data and results of DFT calculations. Reaction of 2 with N-2 gave the dinitrogen complex cis,cis-Ru(N-2)Cl-2(POP-Pr-i) (6), but solutions of 1 under a nitrogen atmosphere showed no evidence of an analogous compound. The different steric requirements of the phosphorus substituents of the POP ligands were identified as the source of the differences in the coordination properties of the POP-Bu-t and POP-iPr complexes 1-6.

  DOI：

  10.1021/om050053v