{Ir(cycloocta-1,5-diene)((p-tolyl)3P)2}SbF6 | 111349-24-7

• 英文名称: {Ir(cycloocta-1,5-diene)((p-tolyl)3P)2}SbF6
• CAS: 111349-24-7
• 化学式: C₅₀H₅₄IrP₂*F₆Sb
• 分子量: 1144.89
• InChiKey: ZNOBRXQBROWVKF-HUZCCYCJSA-H

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

• 作为反应物：
  描述：

  {Ir(cycloocta-1,5-diene)((p-tolyl)3P)2}SbF6 在 氢气 作用下， 以 丙酮 为溶剂， 生成 dihydridobis(acetone)bis(tris(p-tolyl)phosphine)iridium(III) hexafluorophosphate
  参考文献：
  名称：

  烷烃选择性催化脱氢制烯烃

  摘要：

  使用铱配合物作为催化剂，直链和环状烷烃可以通过热和光化学（254 nm）选择性脱氢成相应的烯烃。在光化学情况下，不需要牺牲氢受体，直接释放出 H/sub 2/。最不稳定的烯烃（例如，来自甲基环己烷的亚甲基环己烷）的优先初始形成是通过对金属的氧化加成攻击不受阻碍的 CH 键来解释的。随后的..beta..-消除得到烯烃。催化剂 (IrH/sub 2/(eta/sup 2/-O/sub 2/CCF/sub 3/)(PR/sub 3/)/sub 2/) (4) 的一个关键特征是螯合乙酸酯基团可以打开以允许在烷基氢化物中间体 (IrH(R)(eta/sup 2/-O/sub 2/CCF/sub 3/)(PR/sub 3/)/子 2/)。延长的反应时间导致烯烃逐渐异构化以得到热力学产物（例如，来自甲基环己烷的1-甲基环己烯）。观察到高达 32 次脱氢转换。在热情况下，通过 PAr/sub 2/ 配体的

  DOI：

  10.1021/ja00260a013
• 作为产物：
  描述：

  iridium(I)-(1c,5c-cyclooctadiene) chloride dimer 、 三对苯甲基膦 生成 {Ir(cycloocta-1,5-diene)((p-tolyl)3P)2}SbF6
  参考文献：
  名称：

  CRABTREE R. H.; PARNELL C. P.; URIARTE R. J., ORGANOMETALLICA, 6,(1987) N 4, 696-699

  摘要：

  DOI：

文献信息

• Dehydrogenation of alkanes to arenes by iridium complexes
  作者：Robert H. Crabtree、Charles P. Parnell、Richard J. Uriarte

  DOI：10.1021/om00147a003

  日期：1987.4.1
• Facile reversible metalation in an agostic complex and hydrogenolysis of a metal aryl complex via a dihydrogen complex
  作者：Ana C. Albeniz、Gayle Schulte、Robert H. Crabtree

  DOI：10.1021/om00037a045

  日期：1992.1

  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)HP(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.