hydrido-(1,5-cyclooctadiene)(bis(1,2-diphenylphosphino)ethane)-iridium | 110429-87-3

• 英文名称: hydrido-(1,5-cyclooctadiene)(bis(1,2-diphenylphosphino)ethane)-iridium
• 英文别名: HIr(1,5-cyclooctadiene)(1,2-bis(diphenylphosphino)ethane)；HIr(cod)(dppe)；HIr(1,5-cyclooctadiene)(dppe)
• CAS: 110429-87-3
• 化学式: C₃₄H₃₇IrP₂
• 分子量: 699.835
• InChiKey: LGGGFWKRJSQERC-ONEVTFJLSA-N

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：

  1,2-双(二苯基膦)乙烷 、 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 以 甲醇 为溶剂， 以69%的产率得到hydrido-(1,5-cyclooctadiene)(bis(1,2-diphenylphosphino)ethane)-iridium
  参考文献：
  名称：

  Preparation of IrH(diene)L2 compounds via methoxyiridium complexes: Catalysts for hydrogen transfer reactions

  摘要：

  DOI：

  10.1016/0022-328x(86)80504-6

文献信息

• Ir^I(η⁴-diene) precatalyst activation by strong bases: formation of an anionic Ir^III tetrahydride
  作者：Paven Kisten、Eric Manoury、Agustí Lledós、Adrian C. Whitwood、Jason M. Lynam、John M. Slattery、Simon B. Duckett、Rinaldo Poli

  DOI：10.1039/d2dt04036k

  日期：——

  present in the strong base (KOtBu in benzene or toluene), the COD ligand in 1 is deprotonated, followed by β-H elimination of an IrI–C8H11 intermediate, which leads to complex [IrH(1-κ-4,5,6-η3-C8H10)(dppe)] (4) selectively. This is followed by its reversible isomerisation to 5, which features a different relative orientation of the same ligands (k45 = (3.92 ± 0.11) × 10−4 s−1; k5-4 = (1.39 ± 0.12) × 10−4

  [IrCl(COD)] 2和 dppe 以 1:2 的比例在三种不同条件下的反应进行了详细研究。[IrCl(COD)(dppe)], 1是在没有碱存在的室温下形成的。在室温下存在强碱的情况下，会生成将碳环配体保留在配位层中的氢化物络合物。在异丙醇中，1在添加 KO t Bu 时转化为 [IrH(1,2,5,6-η 2 :η 2 -COD)(dppe)] ( 2 ) ，其中k 12 = (1.11 ± 0.02) × 10 −4 s −1，随后可逆异构化为[IrH(1-κ-4,5,6-η 3 -C8 H 12 )(dppe)] ( 3 ) 其中k 23 = (3.4 ± 0.2) × 10 −4 s −1和k 32 = (1.1 ± 0.3) × 10 −5 s −1以产生平衡 5 : 95 2和3的混合物。然而，当强碱（苯或甲苯中的 KO t Bu）中不存在氢化物源时， 1中的 COD 配体去质子化，随后
• Organoiridium compounds with bidentate phosphines as highly regioselective catalysts for alkynes cyclotrimerization
  作者：Matteo Fabbian、Nazario Marsich、Erica Farnetti

  DOI：10.1016/j.ica.2004.03.033

  日期：2004.7

  The iridium derivatives HIr(cod)(L-L) (cod = 1,5-cyclooctadiene; L-L = Ph2PCH2PPh2 (dppm); Ph2P(CH2)(2)PPh2 (dppe); Ph2P(CH2)(3)PPh2 (dppp); Ph-2(CH2)(4)PPh2 (dppb); o-C6H4(PPh2)(2); Cy2P(CH2)(2)PCy2 (dcpe); o-Me2NC6H4PPh2 (P-NMe2)) and Ir(OMe)(cod)(dppe-F) (dppe-F = (C6F5)(2)P(CH2)(2)P(C6F5)(2)) are active catalysts for the cyclotrimerization of phenylacetylene and substituted derivatives. The nature of the phosphine ligand has a pronounced effect on catalytic activity and selectivity of the reactions: in some cases (L-L = dcpe, dppe-F) mixtures of oligomerization and polymerization products are obtained, in others only cyclomerization is observed, with regioselectivities as high as 100% of the 1,2,4-trisubstituted benzenes in the reactions catalyzed by HIr(cod)(dppm). The observed regioselectivity is discussed in terms of preferential formation of one of the possible metallacyclic intermediates of the catalytic reaction. (C) 2004 Elsevier B.V. All rights reserved.