[6-oxo-4,7-di-(2-trifluoromethylphenyl)-2,3-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese | 383401-37-4

• 英文名称: [6-oxo-4,7-di-(2-trifluoromethylphenyl)-2,3-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese
• CAS: 383401-37-4
• 化学式: C₃₆H₂₁F₆MnO₄
• 分子量: 686.489
• InChiKey: BTYWTACNUXQTHG-SSMZTGFVSA-N

反应信息

• 作为产物：
  描述：

  [1-(2-trifluoromethylphenyl)-2-[(E)-3-(2-trifluoromethylphenyl)prop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese 、 二苯基乙炔 以 四氯化碳 为溶剂， 以35%的产率得到[6-oxo-4,7-di-(2-trifluoromethylphenyl)-2,3-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese
  参考文献：
  名称：

  β-Cyclomanganated 1,5-二苯基戊-1,4-二烯-3-酮和它们的反应与炔烃：路由到η 5 -pyranyl和η 5 -oxocycloheptadienylMn（CO）3个配合物

  摘要：

  将1,5-二苯基-1,4-二-3-酮（4）与苄基五羰基锰环金属化以形成[[1-苯基-2-（（E）-3-苯基丙-2-烯-1-酰基-κ] ø）]乙烯基-κ ç 1 ] tetracarbonylmanganese衍生物（5）。的联接5，在一些情况下，炔烃给出[4-苯基-2-（2-苯基乙烯基）吡喃基-η 5 ] tricarbonylmanganese复合物（6）类似于前面β-manganated查耳酮报道的那些，但在其他情况下可替换的环化途径将炔烃插入CMn键后，会生成[6-氧代-4,7-二苯基环庚-1,4-二烯基-1,2,3,4,5-η]三羰基锰配合物（7）。报道了一种这样的化合物，[6-氧代-2,4,7-三苯基环庚-1,4-二烯基-1,2,3,4,5-η]三羰基锰（7a）的X射线晶体结构测定，由1，5-二苯基戊-1，4-二烯-3-酮和苯乙炔衍生而来。发现7-苯基基团占据了内位，并且提出了

  DOI：

  10.1016/s0022-328x(01)01062-2

文献信息

• Reversible pyranyl complex formation and the mechanism of rearrangement to (η5-6-oxocycloheptadienyl)Mn(CO)3 complexes in the reaction of β-cyclomanganated 1,5-diarylpenta-1,4-dien-3-ones and alkynes; the crystal structure of [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese
  作者：Wade J. Mace、Lyndsay Main、Brian K. Nicholson

  DOI：10.1016/j.jorganchem.2005.04.015

  日期：2005.7

  [1-Phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-kappa O]ethenyl-kappa C-1]tetracarbonylmanganese (1a) reacts with PhCCH in CCl4 at room temperature to form [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-eta(5)]tricarbonylmanganese (2a), whose X-ray crystal structure is reported to complement that of its isomer [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-eta]tricarbonylmanganese (3a), previously obtained from the reaction under reflux; but for la and PhCCPh the pyranyl complex cannot be isolated before rearrangement to the 3a analogue occurs. More forcing reaction conditions for la with Me3SiCCH and for [1-(2-trifluoromethylphenyl)-2-[(E)-3-(2-trifluoromethylphenyl)prop-2-en-1-oyl-kappa O]ethenyl-kappa C-1]tetracarbonylmanganese (1b) with Me3SiCCH and PhCCH give new analogues of 3a where previously only 2a analogues had been isolated.The reaction in CCl4 under reflux of PhCCH and the beta-deuterio analogue of 1a, [1-phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-3d-kappa O]ethenyl-kappa C-1]tetracarbonylmanganese, gave deuteriated 3a with exo-D at the alpha-carbon, C7. This is inconsistent with the Mn-mediated Ph migration mechanism originally proposed to accommodate the endo position of Ph in 3a, and instead it implicates a cyclopropyl carbonyl-addition intermediate or a cyclopropyl acyl-substitution transition state in the key rearrangement step for 2a -> 3a. (c) 2005 Elsevier B.V. All rights reserved.