RuH(dppe)2(MeCN)(1+) | 360768-42-9

• 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: RuH(dppe)2(MeCN)(1+)
• 英文别名: RuH(bis(1,2-diphenylphosphino)ethane)2(MeCN)(1+)
• CAS: 360768-42-9
• 化学式: C₅₄H₅₂NP₄Ru
• 分子量: 939.979
• InChiKey: VBANVHOHQAJBFW-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  RuH(dppe)2(3,3-diphenylphosphinodole)OTf 、 乙腈 以 乙腈 为溶剂， 生成 RuH(dppe)2(MeCN)(1+)
  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

文献信息

• Mechanisms of Reactions of Dihydrogen Complexes:  Formation of <i>trans</i>-[RuH(H₂)(dppe)₂]⁺ and Substitution of Coordinated Dihydrogen
  作者：Manuel G. Basallote、Joaquín Durán、M. Jesús Fernández-Trujillo、M. Angeles Máñez

  DOI：10.1021/ic9902267

  日期：1999.11.1

  The reactions between cis-[RuH(2)(DPPE)(2)] and a number of acids in THF solution (DPPE = Ph(2)PCH(2)CH(2)PPh(2)) show biphasic kinetics, with initial formation of trans-[RuH(H(2))(DPPE)(2)](+) followed by slower substitution of coordinated dihydrogen by the anion of the acid. The formation of the dihydrogen complex is a second-order process that occurs with an inverse kinetic isotope effect and rate

  顺式-[RuH（2）（DPPE）（2）]与许多酸在THF溶液中的反应（DPPE = Ph（2）PCH（2）CH（2）PPh（2））显示出双相动力学，反式[RuH（H（2））（DPPE）（2）]（+）的初始形成，然后由酸的阴离子缓慢取代配位二氢。二氢配合物的形成是第二级过程，发生时具有逆动力学同位素效应，速率常数k（HX）强烈依赖于酸的性质。顺式[RuH（2）（DPPE）（2）]和相关顺式[FeH（2）（PP（3））] [PP（3）的log k（HX）值之间存在线性关系）= P（CH（2）CH（2）PPh（2））（3）]，这会导致两个参数S和R用作衡量二酐对酸的选择性和固有反应性的量度。讨论了对这些参数值的可能贡献，特别是起始配合物异构化的作用和反应物种的碱性。反式-[RuH（H（2））（DPPE）（2）]（+）中的配位二氢的取代是通过一种简单的解离机理发生的，而不是通过先前提议的类似的Fe