tricarbonyl{1-3-η-5-σ-3-(methoxycarbonyl)cyclohept-1-enediyl}iron | 126796-41-6

• 英文名称: tricarbonyl{1-3-η-5-σ-3-(methoxycarbonyl)cyclohept-1-enediyl}iron
• CAS: 126796-41-6
• 化学式: C₁₂H₁₂FeO₅
• 分子量: 292.071
• InChiKey: KYQMOGSVBZGTCR-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  sodium tetrahydroborate 、 tricarbonyl(3-methoxycarbonylcycloheptadienyl)iron hexafluorophosphate 以60%的产率得到tricarbonyl{1-3-η-5-σ-3-(methoxycarbonyl)cyclohept-1-enediyl}iron
  参考文献：
  名称：

  甲氧基羰基取代的环庚二烯基铁三羰基阳离子的制备和反应：添加稳定的烯醇盐亲核试剂期间异常的区域化学

  摘要：

  制备了三羰基（1-甲氧基羰基环庚二烯基）六氟磷酸铁（9）和三羰基（3-甲氧基羰基环庚二烯基）六氟磷酸铁（12），并研究了与一系列亲核试剂的反应。氰化物，硼氢化物和丙二酸烯醇盐都专门添加到（9）的C-2中，主要添加到（12）的C-2中，而Me 2 CuLi，氢氧化物和邻苯二甲酰亚胺钾都在两种配合物的C-1处反应。在添加NaCH（CO 2 Me）2的过程中，区域选择性异常，反映了酯取代基对二烯基-铁系统的显着扰动。

  DOI：

  10.1039/c39890001332

文献信息

• Preparation and reactions of tricarbonyliron complexes of methyl cycloheptadienecarboxylates and methylcycloheptadienes
  作者：Anthony J. Pearson、Marco P. Burello

  DOI：10.1021/om00037a072

  日期：1992.1

  The preparation and reactions with nucleophiles of tricarbonyl[1-(methoxycarbonyl)cycloheptadienylium]iron hexafluorophosphate (7) and tricarbonyl[3-(methoxycarbonyl)cycloheptadienylium]iron hexafluorophosphate (12) were studied. Unusual regioselectivity was observed for the addition of dimethyl malonate enolate to these complexes, viz., exclusively C(2) addition to 7 and predominantly C(2) addition to 12, giving enediyl complexes. Replacement of CO ligand with triphenylphosphine does not affect this regioselectivity. Attempts to rationalize these observations using C-13 NMR spectroscopy and extended Huckel calculations met with limited success. The preparation and reactions of tricarbonyl(1-methylcycloheptadienylium)iron hexafluorophosphate (31) are described. Addition of malonate to 31 proceeds with exclusive formation of the substituted cycloheptadiene complex, thus confirming the marked effect of the ester substituent on the reactivity of complexes 7 and 12.