[Ru(η6-cymene)(ethylenediamine)Cl]BPh4 | 65684-78-8

• 英文名称: [Ru(η6-cymene)(ethylenediamine)Cl]BPh4
• CAS: 65684-78-8
• 化学式: C₁₂H₂₂ClN₂Ru*C₂₄H₂₀B
• 分子量: 650.077
• InChiKey: QVQHUNOUWZLCBV-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：

  thallium(I) hexafluorophosphate 、 [Ru(η6-cymene)(ethylenediamine)Cl]BPh4 以 二氯甲烷 为溶剂， 以98%的产率得到[(η⁶-p-cymene)RuCl(H₂NCH₂CH₂NH₂-N,N)]PF₆
  参考文献：
  名称：

  An Accurate Methodology to Identify the Level of Aggregation in Solution by PGSE NMR Measurements:  The Case of Half-Sandwich Diamino Ruthenium(II) Salts

  摘要：

  The utility of PGSE NMR measurements in determining hydrodynamic radii (r(H)) and volumes (V-H) of small- and medium-size molecules (3 angstrom < r(H) < 6 angstrom) was evaluated by performing measurements for a variety of pure deuterated solvents and their solutions containing the internal standard TMSS [tetrakis(trimethylsilyl)silane] also in the presence of a variable concentration of 3BPh(4). It was found that accurate rH and VH values can be obtained by introducing in the Stokes-Einstein equation (D-t = kT/c pi eta r(H)) not only the correct values for temperature (T) and viscosity (eta) but, particularly, that for the C factor. PGSE NMR measurements were then applied to an investigation of the aggregation tendency of complexes [Ru(eta(6)-cymene)(R1R2NCH2CH2NR1R2)Cl]X (R-1 = R-2 = H, 1; R-1 = H, R-2 = H, 2; R-1 = R-2 = Me, 3; X- = PF6- or BPh4-) in both protic and aprotic solvents with a relative permittivity (epsilon(r)) ranging from 4.81 (chloroform-d) to 32.66 (methanol-d(4)). Compounds I and 2 exhibited a remarkable tendency to aggregate through intercationic N-(HCl)-Cl-... and cation/anion N-(HFPF5-)-F-... hydrogen bonds. In addition to ion pairs, ion triples and ion quadruples were also observed in solution. Compound 3, having no N-H moiety, showed less tendency to aggregate than I and 2, even though it also afforded ion quadruples in apolar and aprotic solvents. Relative anion-cation orientations and arene conformations were investigated by means of H-1-NOESY and F-19,H-1-HOESY NMR spectroscopy. The relative anion-cation position was well-defined, especially for compounds bearing the PF6- counterion, and was modulated by the nature of the N,N ligand. A progressive slackening of the contact aggregates was observed in the series 1-3 that led to a higher mobility of the anion, as indicated by the observation of less specific interionic NOEs.

  DOI：

  10.1021/om050145k
• 作为产物：
  描述：

  [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 四苯硼钠 、 乙二胺 以 甲醇 为溶剂， 以84%的产率得到[Ru(η6-cymene)(ethylenediamine)Cl]BPh4
  参考文献：
  名称：

  An Accurate Methodology to Identify the Level of Aggregation in Solution by PGSE NMR Measurements:  The Case of Half-Sandwich Diamino Ruthenium(II) Salts

  摘要：

  The utility of PGSE NMR measurements in determining hydrodynamic radii (r(H)) and volumes (V-H) of small- and medium-size molecules (3 angstrom < r(H) < 6 angstrom) was evaluated by performing measurements for a variety of pure deuterated solvents and their solutions containing the internal standard TMSS [tetrakis(trimethylsilyl)silane] also in the presence of a variable concentration of 3BPh(4). It was found that accurate rH and VH values can be obtained by introducing in the Stokes-Einstein equation (D-t = kT/c pi eta r(H)) not only the correct values for temperature (T) and viscosity (eta) but, particularly, that for the C factor. PGSE NMR measurements were then applied to an investigation of the aggregation tendency of complexes [Ru(eta(6)-cymene)(R1R2NCH2CH2NR1R2)Cl]X (R-1 = R-2 = H, 1; R-1 = H, R-2 = H, 2; R-1 = R-2 = Me, 3; X- = PF6- or BPh4-) in both protic and aprotic solvents with a relative permittivity (epsilon(r)) ranging from 4.81 (chloroform-d) to 32.66 (methanol-d(4)). Compounds I and 2 exhibited a remarkable tendency to aggregate through intercationic N-(HCl)-Cl-... and cation/anion N-(HFPF5-)-F-... hydrogen bonds. In addition to ion pairs, ion triples and ion quadruples were also observed in solution. Compound 3, having no N-H moiety, showed less tendency to aggregate than I and 2, even though it also afforded ion quadruples in apolar and aprotic solvents. Relative anion-cation orientations and arene conformations were investigated by means of H-1-NOESY and F-19,H-1-HOESY NMR spectroscopy. The relative anion-cation position was well-defined, especially for compounds bearing the PF6- counterion, and was modulated by the nature of the N,N ligand. A progressive slackening of the contact aggregates was observed in the series 1-3 that led to a higher mobility of the anion, as indicated by the observation of less specific interionic NOEs.

  DOI：

  10.1021/om050145k