| 154593-29-0

• CAS: 154593-29-0
• 化学式: C₄₇H₄₇IrP₃*F₆P
• 分子量: 1042.0
• InChiKey: IXISCYGMZKXDIY-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：
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• 环数：
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• 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

• 作为产物：
  描述：

  thallium(I) hexafluorophosphate 、 乙烯 、 以 四氢呋喃 为溶剂， 以20%的产率得到
  参考文献：
  名称：

  Molecular Solid-Gas Organometallic Chemistry. Catalytic and Stoichiometric Iridium-Assisted C-C Bond-Forming Reactions Involving Ethyne and Ethene

  摘要：

  Treatment of crystals of the (eta2-ethene)dihydride complex [(triphos)Ir(H)2(C2H4)]BPh4 (1; triphos = MeC(CH2PPh2)3) with ethyne (4 atm) at 70-degrees-C for 3 h results in evolution of ethene and but-2-ene and formation of five different organometallic products, namely the eta4-benzene complex [(triphos)Ir(eta4-C6H6)]BPh4 (2), the eta4-buta-1,3-diene complex [(triphos)Ir(eta4-C4H6)]BPh4 (3), the eta4-cyclohexa-1,3-diene complex [(triphos)Ir(eta4-C6H8)]BPh4 (4), and the crotyl hydride isomers [(triphos)Ir(H) (eta3-MeC3H4)]BPh4 (5-anti and 5-syn) in a kinetic product ratio of 35:5:23:28:9. At 100-degrees-C, the solid-gas reaction produces catalytic amounts of benzene, the catalyst precursor being the eta4-benzene complex 2. Temperature-programmed reactions carried out in a flow reactor and the use of isolated complexes in independent solid-gas reactions permit mechanistic conclusions which account for the varied organic and organometallic products. The ethene ligand in 1 is an essential ingredient for both cyclotrimerization and cooligomerization reactions of ethyne, which are traversed by eta3-crotyl complexes. Conversely, the ethene ligand is a competitive inhibitor for the reductive dimerization of ethyne to buta-1,3-diene, for which the two hydride ligands are mandatory. Comparison with fluid solution-phase systems provides evidence for the control exerted by the constraining environment of the crystal lattice on the solid-gas reactions.

  DOI：

  10.1021/om00016a020