[pentamethylcyclopentadienyl*Ir(2,2’-bipyridine)H]PF6 | 519140-48-8

• 英文名称: [pentamethylcyclopentadienyl*Ir(2,2’-bipyridine)H]PF6
• 英文别名: [Cp*Ir(2,2’-bipyridine)H]PF6；[Cp*Ir(bpy)H][PF₆]；[(η5-C5Me5)Ir(2,2'-bipyridine)H]PF6；[(Cp*)Ir(2,2'-bipyridine)(H)][PF6]；[(Cp*)Ir(bpy)(H)][PF6]
• CAS: 519140-48-8
• 化学式: C₂₀H₂₄IrN₂*F₆P
• 分子量: 629.608
• InChiKey: KWXKMORGABRGAU-UHFFFAOYSA-N

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：

  [pentamethylcyclopentadienyl*Ir(2,2’-bipyridine)H]PF6 在 溶剂黄146 作用下， 以 乙腈 为溶剂， 生成 氢气
  参考文献：
  名称：

  由双金属自淬火机制引发的高效光化学双氢生成

  摘要：

  人工光合作用依赖于光吸收与化学燃料生成的耦合。[Cp*Ir(bpy)H]+ (1) 可见光驱动 H2 产生的机理研究揭示了一种新的高效途径，用于整合光吸收与键形成。1 与质子源的净反应产生 H2，但激发态猝灭的速率令人惊讶地与酸无关，并且没有显示可观察到的氘动力学同位素效应。时间分辨光致发光和标记研究与通过电子转移进行的扩散限制双金属自淬火一致。因此，随着 1 浓度的增加，H2 释放的量子产率几乎达到 1。这种独特的光化学 H2 生成途径提供了对由 1 催化的转化的深入了解。

  DOI：

  10.1021/jacs.6b08701
• 作为产物：
  描述：

  甲酸 、 [pentamethylcyclopentadienylIr(2,2'-bipyridine)Cl]Cl 以 水 为溶剂， 反应 0.75h， 以66%的产率得到[pentamethylcyclopentadienyl*Ir(2,2’-bipyridine)H]PF6
  参考文献：
  名称：

  Hydrogenation of Carboxylic Acids Catalyzed by Half-Sandwich Complexes of Iridium and Rhodium

  摘要：

  A series of half-sandwich Ir and Rh compounds are demonstrated to be competent catalysts for the hydrogenation of carboxylic acids under relatively mild conditions. Of the structurally diverse group of catalysts tested for activity, a Cp*Ir complex supported by an electron-releasing 2,2'-bipyridine ligand was the most active. Higher activity was achieved with employment of Bronsted or Lewis acid promoters. Mechanistic studies suggest a possible reaction pathway involving activated carboxylic acid substrates. The hydrogenation reaction was shown to be general to a variety of aliphatic acids.

  DOI：

  10.1021/ja408149n
• 作为试剂：
  描述：

  溶剂黄146 在 [pentamethylcyclopentadienyl*Ir(2,2’-bipyridine)H]PF6 、 氢气 作用下， 120.0 ℃ 、2.7 MPa 条件下， 反应 65.0h， 生成 乙醇 、 乙酸乙酯
  参考文献：
  名称：

  Hydrogenation of Carboxylic Acids Catalyzed by Half-Sandwich Complexes of Iridium and Rhodium

  摘要：

  A series of half-sandwich Ir and Rh compounds are demonstrated to be competent catalysts for the hydrogenation of carboxylic acids under relatively mild conditions. Of the structurally diverse group of catalysts tested for activity, a Cp*Ir complex supported by an electron-releasing 2,2'-bipyridine ligand was the most active. Higher activity was achieved with employment of Bronsted or Lewis acid promoters. Mechanistic studies suggest a possible reaction pathway involving activated carboxylic acid substrates. The hydrogenation reaction was shown to be general to a variety of aliphatic acids.

  DOI：

  10.1021/ja408149n

文献信息

• Isolation and Crystal Structure of a Water-Soluble Iridium Hydride:  A Robust and Highly Active Catalyst for Acid-Catalyzed Transfer Hydrogenations of Carbonyl Compounds in Acidic Media
  作者：Tsutomu Abura、Seiji Ogo、Yoshihito Watanabe、Shunichi Fukuzumi

  DOI：10.1021/ja0288237

  日期：2003.4.1

  complex [Cp*Ir(III)(bpy)H](+) (1, Cp* = eta(5)-C(5)Me(5), bpy = 2,2'-bipyridine) that serves as a robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds at pH 2.0-3.0 at 70 degrees C. The catalyst 1 was synthesized from the reaction of a precatalyst [Cp*Ir(III)(bpy)(OH(2))](2+) (2) with hydrogen donors HCOOX (X = H or Na) in H(2)O under controlled conditions (2

  本文报道了水溶性氢化物复合物 [Cp*Ir(III)(bpy)H](+) (1, Cp* = eta(5)-C(5)Me(5), bpy = 2,2'-联吡啶）作为一种稳健且高活性的催化剂，用于在 pH 2.0-3.0 和 70 摄氏度下羰基化合物的酸催化转移氢化。催化剂 1 由预催化剂 [Cp *Ir(III)(bpy)(OH(2))](2+) (2) 与氢供体 HCOOX（X = H 或 Na）在 H(2)O 中在受控条件下 (2.0 < pH < 6.0, 25摄氏度），这避免了低于 pH 值约 1 的氢化配体的质子化。1.0 和 2 以上 pH 值的水配体去质子化。6.0（pK(a) 值为 2 = 6.6）。X 射线分析表明配合物 1 采用扭曲的八面体几何形状，其中 Ir 原子由一个 eta(5)-Cp*、一个双齿 bpy 配位，和一个占据键位的末端氢化配体。1 的分离使我们能够研究
• Mechanistic investigation of CO2 hydrogenation by Ru(ii) and Ir(iii) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step
  作者：Seiji Ogo、Ryota Kabe、Hideki Hayashi、Ryosuke Harada、Shunichi Fukuzumi

  DOI：10.1039/b607993h

  日期：——

  bpy (5) and 4,4′-OMe-bpy (6)} act as catalysts for hydrogenation of CO2 into HCOOH at pH 3.0 in H2O. The active hydride catalysts cannot be observed in the hydrogenation of CO2 with the ruthenium complexes, whereas the active hydride catalysts, [Cp*IrIII(L)(H)]+ L = bpy (7) and 4,4′-OMe-bpy (8)}, have successfully been isolated after the hydrogenation of CO2 with the iridium complexes. The key to the

  钌水性络合物[（η 6 -C 6我6）的Ru II（L）（OH 2）] 2+ L =py（1）和4,4'-OMe-bpy（2），py = 2,2'-联吡啶，4,4'-OMe-bpy = 4,4'-二甲氧基-2,2'-联吡啶}和铱水性络合物的[Cp *铱III（L）（OH 2）] 2+ 的Cp * =η 5 -C 5我5，L =py（5）和4,4'-OMe-bpy（6）}充当催化剂 为了 氢化在pH 3.0中将CO 2转化为HCOOH高氧2。活跃的氢化物 催化剂用钌配合物在CO 2加氢中无法观察到氢化物 催化剂，[Cp * Ir III（L）（H）] + L =py（7）和4,4'-OMe-bpy（8）}已成功地用铱络合物将CO 2氢化后分离出来。主动隔离成功的关键氢化物 催化剂是活性炭形成过程中CO 2催化加氢过程中决定速率的步骤的变化氢化物 催化剂[（η 6 -C 6我6）的Ru II（L）（H）]