[(η5-C5Me5)Ir(H)(μ-bis(dimethylphosphine)methane)(μ-H)(η5-C5Me5)Ir(3-Fur)][OTf] | 620178-96-3

• 英文名称: [(η5-C5Me5)Ir(H)(μ-bis(dimethylphosphine)methane)(μ-H)(η5-C5Me5)Ir(3-Fur)][OTf]
• 英文别名: [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Cp*Ir)(2-Fur)](OTf)；[(Cp*Ir)(H)(μ-bis(dimethylphosphino)methane)(μ-H)(Cp*Ir)(2-Fur)](OTf)；[Ir2H(3-Fur)(η5-C5Me5)2(μ-dmpm)(μ-H)](OTf)；[Ir2H(3-furyl)(η5-C5Me5)2(μ-bis(dimethylphosphino)methane)(μ-hydrido)](triflate)
• CAS: 620178-96-3
• 化学式: CF₃O₃S*C₂₉H₄₉Ir₂OP₂
• 分子量: 1009.17
• InChiKey: GICBSLONZYVPNU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  呋喃 、 [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Cp*Ir)(Ph)](OTf) 以 neat (no solvent) 为溶剂， 生成 [(η5-C5Me5)Ir(H)(μ-bis(dimethylphosphine)methane)(μ-H)(η5-C5Me5)Ir(3-Fur)][OTf]
  参考文献：
  名称：

  Inter- and Intramolecular Activation of Aromatic C−H Bonds by Diphosphine and Hydrido-Bridged Dinuclear Iridium Complexes

  摘要：

  Reactions of [(Cp*Ir)2(mu-dmpm)(mu-H)2]2+ (1) with NaOtBu in aromatic solvent at room temperature give [(Cp*Ir)(H)(mu-dmpm)(mu-H)(Cp*Ir)(Ar)]+ [Ar = Ph (3), p-Tol (4a), m-Tol (4b), 2-furanyl (5a), 3-furanyl (5b)] via intermolecular aromatic C-H activation. Treatment of [(Cp*Ir)2(mu-dppm)(mu-H)2]2+ (2) with base (Et2NH) results in intramolecular C-H activation of the phenyl group in the dppm ligand to give [(Cp*Ir)(H){mu-PPh(C6H4)CH2PPh2}(mu-H)(Cp*Ir)]+ (6). The structures of 3, 5a, and 6 have been determined by X-ray diffraction methods.

  DOI：

  10.1021/ja036929b

文献信息

• C–H activation on a diphosphine and hydrido-bridged diiridium complex: generation and detection of an active IrII–IrII species [(Cp*Ir)2(μ-dmpm)(μ-H)]+
  作者：Yoshinori Takahashi、Mitsuru Nonogawa、Ken-ichi Fujita、Ryohei Yamaguchi

  DOI：10.1039/b803626h

  日期：——

  Reaction of [Cp*Ir(μ-H)]2 (5) (Cp* = η5-C5Me5) with bis(dimethylphosphino)methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir)2(μ-dmpm)(μ-H)2] (3). Treatment of 3 with methyl triflate at −30 °C results in the formation of [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Me)(IrCp*)][OTf] (6). Warming a solution of 6 above 0 °C brings about predominant generation of 32e− IrII–IrII species [(Cp*Ir)(μ-dmpm)(μ-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 °C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(μ-Me2PCH2PMeCH2)(μ-H)(IrCp*)][OTf] (8), which is formed by intramolecular oxidative addition of the methyl C–H bond of the dmpm ligand. Intermolecular C–H bond activation reactions with 7 are also examined. Reactions of 7 with aromatic molecules (benzene, toluene, furan, and pyridine) at room temperature result in the smooth sp2 C–H activation to give [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H)(μ-dmpm)(μ-C5H4N)(H)(IrCp*)][OTf] (12), respectively. Complex 7 also reacts with cyclopentene at 0 °C to give [(Cp*Ir)(H)(μ-dmpm)(μ-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis.

  Cp*Ir(δ-H)]2 (5) (Cp* = δ-5-C5Me5) 与双(二甲基膦)甲烷 (dmPM) 反应，生成新的中性二铱络合物 [(Cp*Ir)2(δ-dmPM)(¼-H)2] (3)。在 30 °C时用三氯甲烷处理3，会生成[(Cp*Ir)(H)(δ-dmPM)(δ-H)(Me)(IrCp*)][OTf]（6）。将 6 的溶液加热到 0 °C 以上，主要生成 32eâ IrIIâIrII 物种[(Cp*Ir)(δ-dmPM)(δ-H)(IrCp*)][OTf]（7）。将 7 的溶液进一步加热至 30 °C 14 小时后，定量形成了新的复合物[(Cp*Ir)(H)(δ-Me2PCH2PMeCH2)(δ-H)(IrCp*)][OTf]（8），它是由 dmPM 配体的甲基 CâH 键分子内氧化加成形成的。此外，还研究了 7 的分子间 CâH 键活化反应。在室温下，7 与芳香分子（苯、甲苯、呋喃和吡啶）发生反应，顺利发生 sp2 CâH 活化反应，生成[(Cp*Ir)(H)(δ-dmPM)(¼-H)(Ar)(IrCp*)][OTf]（Ar = Ph (9)；Ar = m-Tol (10a) 或 p-Tol (10b)；Ar = 2-Fur (11)）和[(Cp*Ir)(H)(δ-dmPM)(δ-C5H4N)(H)(IrCp*)][OTf]（12）。络合物 7 也会在 0 °C 与环戊烯反应，生成[(Cp*Ir)(H)(δ-dmPM)(δ-H)(1-环戊烯基)(IrCp*)][OTf]（13）。3、8 和 12 的结构已通过 X 射线分析得到证实。
• Activation of C–H and H–H bonds by dinuclear iridium complexes. Oxidative addition to highly active unsaturated 32e− diiridium species
  作者：Ken-ichi Fujita、Yoshinori Takahashi、Hirohide Nakaguma、Taro Hamada、Ryohei Yamaguchi

  DOI：10.1016/j.jorganchem.2008.07.032

  日期：2008.10

  1 with NaOtBu in dichloromethane under carbon monoxide (1 atm) gives a carbonyl-bridged IrII–IrII complex, [(Cp∗Ir)2(μ-dmpm)(μ-H)(μ-CO)][OTf] (8-OTf). These results strongly suggest that the active species in C–H and H–H bond activation starting with 1 and 2 would be unsaturated 32e− diiridium species. The structures of 3, 5a, 6, 7, and 8-BPh4 have been determined by X-ray diffraction methods.

  [（Cp ∗ Ir）2（μ-dmpm）（μ-H）2 ] [OTf] 2（1）与NaO t Bu在室温下在芳族溶剂中的反应得到[（Cp ∗ Ir）（H）（μ -dmpm）（μ-H）（Cp ∗ Ir）（Ar）] [OTf] [Ar = Ph（3），p -Tol（4a），m -Tol（4b），2-呋喃基（5a），3 -呋喃基（5b）]通过分子间芳香族C – H活化。用弱碱（Et）处理[（Cp ∗ Ir）2（μ-dppm）（μ-H）2 ] [OTf] 2（2）2 NH）导致分子内C–H活化dppm配体中的苯基，得到[（Cp ∗ Ir）（H）μ-PPh（C 6 H 4）CH 2 PPh 2 }（μ-H）（ Cp * Ir）] [OTf]（6）。1在H 2（1 atm）下与四氢呋喃中的NaO t Bu反应，导致H – H键活化，得到[（Cp ∗ Ir）（H）} 2（μ-dmpm）（μ-H）] [O