FeH(dppe)2(MeCN)OTf | 252659-36-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: FeH(dppe)2(MeCN)OTf
• 英文别名: FeH(bis(1,2-diphenylphosphino)ethane)2(MeCN)OTf
• CAS: 252659-36-2
• 化学式: CF₃O₃S*C₅₄H₅₂FeNP₄
• 分子量: 1043.83
• InChiKey: SVZLOYGQWJKIQT-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  FeH(dppe)2(3,3-diphenylphosphinodole)OTf*THF 、 乙腈 以 乙腈 为溶剂， 生成 FeH(dppe)2(MeCN)OTf
  参考文献：
  名称：

  A Synthetic Cycle for the Ruthenium-Promoted Formation of 1H-Phosphindoles from Phosphaalkynes

  摘要：

  Beginning with inexpensive and commercially available starting materials, a rational synthesis for the new phosphaalkyne Ph3C-C P ( 1) is presented. Coordination of 1 to group 8 transition metal centers furnishes the eta(1)-complexes [ MH( dppe)(2)( Ph3CC P)] OTf, where M) Fe ( 3) or Ru ( 4) ( dppe) bis-1,2-diphenylphosphinoethane). Treatment of 3 or 4 with a strong acid cyclizes the coordinated phosphaalkyne and is the first example of an electrophilic aromatic substitution reaction in which the electrophile is a low coordinate phosphorus. With the aid of DFT calculations, we were able to gain a more thorough understanding of the energetics and mechanism of this new cyclization reaction. Thermolysis of the iron-3,3-diphenyl-3H-phosphindole adduct ( 6) in CH3CN results in quantitative formation of the free 3H-phosphindole ( 7). Alternatively, when ruthenium-3,3-diphenyl-3H-phosphindole adduct ( 5) is irradiated, a photochemical rearrangement occurs furnishing 2,3-diphenyl-1H-phosphindole ( 9). Mechanistic work is presented that provides an explanation for this transformation. Compounds 1, 3, 5, and 9 have been characterized by single X-ray diffraction studies. Finally, a synthetic cycle for the conversion of 1 to 1H-phosphindole 9 has been developed that recycles the ruthenium cation [ RuH( dppe)(2)](+).

  DOI：

  10.1021/ja0651198