{Ir(diphpyH)H(P(p-C6H4CH3)3)2}SbF6 | 137466-24-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: {Ir(diphpyH)H(P(p-C6H4CH3)3)2}SbF6
• CAS: 137466-24-1
• 化学式: C₅₉H₅₅IrNP₂*F₆Sb
• 分子量: 1268.0
• InChiKey: YHGUDRKGJNFRTB-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为反应物：
  描述：

  {Ir(diphpyH)H(P(p-C6H4CH3)3)2}SbF6 在 H₂ 作用下， 以 二氯甲烷-D2 为溶剂， 生成 、
  参考文献：
  名称：

  Facile reversible metalation in an agostic complex and hydrogenolysis of a metal aryl complex via a dihydrogen complex

  摘要：

  2,6-Diarylpyridines, 2,6-(p-C6H4R')2C5H3N (diarpyH2: R' = H, diphypyH2; R' = CH3, ditolpyH2) react with [(COD)Ir(PR3)2]X (1; PR3 = PPh3, P(p-C6H4CH3)3, P(p-C6H4F)3, PPh2Me, P-n-Bu3; X = SbF6-, BF4-) under H-2 to give complexes with the stoichiometry [Ir(diarpyH)H(PR3)2]X (2a-f). The X-ray crystal structure for [Ir(diphpyH)H{P(p-C6H4CH3)3}2]SbF6 (2b) shows that one phenyl group of the diphypyH is orthometalated and the other is bound to the Ir via an agostic C-H bond. The Ir...C distance of the Ir...H-C group is 2.69 angstrom, indicating a moderately strong agostic interaction. 2b crystallizes in the triclinic system, space group P1BAR, with a = 11.072 (2) angstrom, b = 14.450 (2) angstrom, c = 17.227 (2) angstrom, alpha = 92.76 (1)-degrees, beta = 105.04 (1)-degrees, gamma = 95.00 (1)-degrees, and Z = 2. The complexes 2a-f show dynamic behavior in solution, consistent with rapid oxidative addition of the agostic C-H bond together with reductive elimination of the aryl hydride. Ligands like CO or CH3CN displace the agostic C-H in 2a to give [Ir(diphpyH)HL(PPh3)2]SbF6 (L = CO, 3; CH3CN, 4). H-2 reacts with 2d (PR3 = PPh2Me) and 2e (PR3 = P-n-Bu3) in the same way to give the dihydrogen complexes [Ir(diphpyH)H(eta(2)-H-2)(PR3)2]SbF6 (5d,e). Reversible Ir-Ar hydrogenolysis occurs with H-2 for 2a-c and 2f; an equilibrium between the dihydrogen complex 5 and the hydrogenolysis product [Ir(diphpyH2)(H)2(PR3)2]SbF6 (6) is observed at low temperatures. For a given diarpyH ligand, less basic phosphines favor the hydrogenolysis product. Longer treatment of 2a with H-2 leads to complete displacement of the diarpyH2 ligand from the metal.

  DOI：

  10.1021/om00037a045
• 作为产物：
  描述：

  {Ir(cycloocta-1,5-diene)((p-tolyl)3P)2}SbF6 、 2,6-二苯基吡啶 在 H₂ 作用下， 以 二氯甲烷 为溶剂， 生成 {Ir(diphpyH)H(P(p-C6H4CH3)3)2}SbF6
  参考文献：
  名称：

  Facile reversible metalation in an agostic complex and hydrogenolysis of a metal aryl complex via a dihydrogen complex

  摘要：

  2,6-Diarylpyridines, 2,6-(p-C6H4R')2C5H3N (diarpyH2: R' = H, diphypyH2; R' = CH3, ditolpyH2) react with [(COD)Ir(PR3)2]X (1; PR3 = PPh3, P(p-C6H4CH3)3, P(p-C6H4F)3, PPh2Me, P-n-Bu3; X = SbF6-, BF4-) under H-2 to give complexes with the stoichiometry [Ir(diarpyH)H(PR3)2]X (2a-f). The X-ray crystal structure for [Ir(diphpyH)H{P(p-C6H4CH3)3}2]SbF6 (2b) shows that one phenyl group of the diphypyH is orthometalated and the other is bound to the Ir via an agostic C-H bond. The Ir...C distance of the Ir...H-C group is 2.69 angstrom, indicating a moderately strong agostic interaction. 2b crystallizes in the triclinic system, space group P1BAR, with a = 11.072 (2) angstrom, b = 14.450 (2) angstrom, c = 17.227 (2) angstrom, alpha = 92.76 (1)-degrees, beta = 105.04 (1)-degrees, gamma = 95.00 (1)-degrees, and Z = 2. The complexes 2a-f show dynamic behavior in solution, consistent with rapid oxidative addition of the agostic C-H bond together with reductive elimination of the aryl hydride. Ligands like CO or CH3CN displace the agostic C-H in 2a to give [Ir(diphpyH)HL(PPh3)2]SbF6 (L = CO, 3; CH3CN, 4). H-2 reacts with 2d (PR3 = PPh2Me) and 2e (PR3 = P-n-Bu3) in the same way to give the dihydrogen complexes [Ir(diphpyH)H(eta(2)-H-2)(PR3)2]SbF6 (5d,e). Reversible Ir-Ar hydrogenolysis occurs with H-2 for 2a-c and 2f; an equilibrium between the dihydrogen complex 5 and the hydrogenolysis product [Ir(diphpyH2)(H)2(PR3)2]SbF6 (6) is observed at low temperatures. For a given diarpyH ligand, less basic phosphines favor the hydrogenolysis product. Longer treatment of 2a with H-2 leads to complete displacement of the diarpyH2 ligand from the metal.

  DOI：

  10.1021/om00037a045