[Ru(η5-C5H5)(6,6'-diamino-2,2'-bipyridine)(CH3CN)](OTf) | 1471401-53-2

• 英文名称: [Ru(η5-C5H5)(6,6'-diamino-2,2'-bipyridine)(CH3CN)](OTf)
• 英文别名: [Ru(η⁵-C5H5)(6,6'-diamino-2,2'-bipyridine)(CH3CN)](OTf)
• CAS: 1471401-53-2
• 化学式: CF₃O₃S*C₁₇H₁₈N₅Ru
• 分子量: 542.504
• InChiKey: QKSPVUQBCBUDEB-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：

  氘代乙腈 、 [Ru(η5-C5H5)(6,6'-diamino-2,2'-bipyridine)(CH3CN)](OTf) 生成 [Ru(η⁵-C5H5)(6,6'-diamino-2,2'-bipyridine)(CD3CN)]OTf
  参考文献：
  名称：

  Comparison of the Catalytic Activity of [(η⁵-C₅H₅)Ru(2,2′-bipyridine)(L)]OTf versus [(η⁵-C₅H₅)Ru(6,6′-diamino-2,2′-bipyridine)(L)]OTf (L = labile ligand) in the Hydrogenation of Cyclohexanone. Evidence for the Presence of a Metal–Ligand Bifunctional Mechanism under Acidic Conditions

  摘要：

  The two title complexes as well as the dimeric complex [Ru(II)(eta(5)-C5H5)(6,6'-diamino-2,2'-bipyridine)12(OTf)(2) have been synthesized and characterized by NMR and single-crystal X-ray crystallography. The direct structural comparison of the 2,2'-bipyridine and 6,6'-diamino-2,2'-bipyridine complexes suggests that the electronic and steric environments of the ruthenium centers in both complexes are essentially equivalent, providing for a unique opportunity to probe the influence of the noncoordinated amine substituent on the relative reactivity and catalytic activity of the complexes. Opposite to what would be anticipated on the basis of steric effects, the bulkier amine-substituted ligand results in a catalyst showing substantially higher activity in the hydrogenation of cyclohexanone in acidic medium, which is attributed to the operation of a metal ligand bifunctional hydrogenation mechanism mediated by the amine substituents in their protonated form acting as proton shuttles.

  DOI：

  10.1021/om400871v
• 作为产物：
  描述：

  2,2'-二吡啶-6,6'-二胺 、 [Cp*Ru(CH3CN)3]OTf 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 以94%的产率得到[Ru(η⁵-C5H5)(6,6'-diamino-2,2'-bipyridine)]2(OTf)2
  参考文献：
  名称：

  Comparison of the Catalytic Activity of [(η⁵-C₅H₅)Ru(2,2′-bipyridine)(L)]OTf versus [(η⁵-C₅H₅)Ru(6,6′-diamino-2,2′-bipyridine)(L)]OTf (L = labile ligand) in the Hydrogenation of Cyclohexanone. Evidence for the Presence of a Metal–Ligand Bifunctional Mechanism under Acidic Conditions

  摘要：

  The two title complexes as well as the dimeric complex [Ru(II)(eta(5)-C5H5)(6,6'-diamino-2,2'-bipyridine)12(OTf)(2) have been synthesized and characterized by NMR and single-crystal X-ray crystallography. The direct structural comparison of the 2,2'-bipyridine and 6,6'-diamino-2,2'-bipyridine complexes suggests that the electronic and steric environments of the ruthenium centers in both complexes are essentially equivalent, providing for a unique opportunity to probe the influence of the noncoordinated amine substituent on the relative reactivity and catalytic activity of the complexes. Opposite to what would be anticipated on the basis of steric effects, the bulkier amine-substituted ligand results in a catalyst showing substantially higher activity in the hydrogenation of cyclohexanone in acidic medium, which is attributed to the operation of a metal ligand bifunctional hydrogenation mechanism mediated by the amine substituents in their protonated form acting as proton shuttles.

  DOI：

  10.1021/om400871v
• 作为试剂：
  描述：

  环己酮 在 三氟甲磺酸 、 [Ru(η5-C5H5)(6,6'-diamino-2,2'-bipyridine)(CH3CN)](OTf) 、 [Ru(η⁵-C5H5)(6,6'-diamino-2,2'-bipyridine)]2(OTf)2 、 氢气 作用下， 175.0 ℃ 、6.21 MPa 条件下， 反应 10.0h， 以63%的产率得到环己醇
  参考文献：
  名称：

  Comparison of the Catalytic Activity of [(η⁵-C₅H₅)Ru(2,2′-bipyridine)(L)]OTf versus [(η⁵-C₅H₅)Ru(6,6′-diamino-2,2′-bipyridine)(L)]OTf (L = labile ligand) in the Hydrogenation of Cyclohexanone. Evidence for the Presence of a Metal–Ligand Bifunctional Mechanism under Acidic Conditions

  摘要：

  The two title complexes as well as the dimeric complex [Ru(II)(eta(5)-C5H5)(6,6'-diamino-2,2'-bipyridine)12(OTf)(2) have been synthesized and characterized by NMR and single-crystal X-ray crystallography. The direct structural comparison of the 2,2'-bipyridine and 6,6'-diamino-2,2'-bipyridine complexes suggests that the electronic and steric environments of the ruthenium centers in both complexes are essentially equivalent, providing for a unique opportunity to probe the influence of the noncoordinated amine substituent on the relative reactivity and catalytic activity of the complexes. Opposite to what would be anticipated on the basis of steric effects, the bulkier amine-substituted ligand results in a catalyst showing substantially higher activity in the hydrogenation of cyclohexanone in acidic medium, which is attributed to the operation of a metal ligand bifunctional hydrogenation mechanism mediated by the amine substituents in their protonated form acting as proton shuttles.

  DOI：

  10.1021/om400871v