Ph2C5H2O(CH(ferrocenyl)) | 1091631-82-1

• 英文名称: Ph2C5H2O(CH(ferrocenyl))
• 英文别名: Ph2C5H2O(CHFc)
• CAS: 1091631-82-1
• 化学式: C₂₈H₂₂FeO
• 分子量: 430.329
• InChiKey: CHKUEJKKOLQSFJ-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：
  None
• 环数：
  None
• 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

• 作为反应物：
  描述：

  Ph2C5H2O(CH(ferrocenyl)) 以 not given 为溶剂， 生成 [Ph2C5H2OCH(ferrocenyl)CH(ferrocenyl)C5H2OPh2](2+)
  参考文献：
  名称：

  Diferrocenylbispyrylium Salts and Electron-Rich Diferrocenylbispyran from Oxidative Coupling of Ferrocenylpyran. Induced Electron Transfer C−C Bond Making/Breaking Involving a Metallocenyl Radical Intermediate

  摘要：

  Electrochemical or chemical dimerization of electronrich ferrocenylmethylenepyran 1 gave the first dimetallocenylbispyrylium salt 2 known today, through a reverse process that implies reductive C-C bond breaking. Deprotonation of the bispyrylium salt 2 afforded extended electron-rich diferrocenyl bispyran 3, which was subsequently reversibly oxidized to diferrocenyl bispyrylium salt 4. This study constitutes a new system in which two ox/red sequences of different nature were separated by proton/deprotonation steps.

  DOI：

  10.1021/om800638q
• 作为产物：
  描述：

  [Ph2C5H2OCH(ferrocenyl)CH(ferrocenyl)C5H2OPh2](2+) 以 not given 为溶剂， 生成 Ph2C5H2O(CH(ferrocenyl))
  参考文献：
  名称：

  Diferrocenylbispyrylium Salts and Electron-Rich Diferrocenylbispyran from Oxidative Coupling of Ferrocenylpyran. Induced Electron Transfer C−C Bond Making/Breaking Involving a Metallocenyl Radical Intermediate

  摘要：

  Electrochemical or chemical dimerization of electronrich ferrocenylmethylenepyran 1 gave the first dimetallocenylbispyrylium salt 2 known today, through a reverse process that implies reductive C-C bond breaking. Deprotonation of the bispyrylium salt 2 afforded extended electron-rich diferrocenyl bispyran 3, which was subsequently reversibly oxidized to diferrocenyl bispyrylium salt 4. This study constitutes a new system in which two ox/red sequences of different nature were separated by proton/deprotonation steps.

  DOI：

  10.1021/om800638q

文献信息

• Anisyl and ferrocenyl adducts of methylenepyran-containing β-diketone: Synthesis, spectral, structural, and redox properties
  作者：Néstor Novoa、Thierry Roisnel、Vincent Dorcet、Jean-René Hamon、David Carrillo、Carolina Manzur、Françoise Robin-Le Guen、Nolwenn Cabon

  DOI：10.1016/j.jorganchem.2014.03.029

  日期：2014.7

  pseudo-aromatic keto–enol ring, confirmed by the crystal structure of 4. Cyclic voltammetric measurements revealed that all the compounds undergo a single one-electron oxidation, localized presumably at the methylenepyran unit. This first oxidation generates a radical cation that undergoes an intermolecular C–C bond coupling to form the corresponding dimer. Anodically shifted to the first oxidation

  原位生成的[2,6-二苯基-4 H-吡喃-4-基磷烷]与4-甲酰基苯甲酸甲酯之间的维蒂希反应得到了甲基[4-（（2,6-二苯基-4 H-吡喃-4-亚基）]苯甲酸甲酯前体2的产率为75％。含亚甲基吡喃的β-二酮3和4的茴香基和二茂铁基加合物分别由t- BuO - K +作为碱性引发剂，通过前体2与4-甲氧基苯乙酮或乙酰基二茂铁之间的碱催化Claisen缩合反应制备。β-二酮3和4分别以50％的收率分离为橙色和深红色结晶固体。乙酰衍生物6，1-乙酰基-1'- methylenepyranyl二茂铁，合成以下父ferrocenylmethylenepyran经典的Friedel-Crafts酰化反应5，并在61％的产率，为红色粉末微晶分离。富电子的乙酰基络合物6和乙酸乙酰基酯之间的缩合反应，使用二异丙基氨基化锂作为活性碱引发剂，提供了含亚铁茂基亚甲基吡喃的β-二酮，1-（1,3-二氧代丁基）-1'-[（2，分离得到6-二苯基-4
• Diferrocenylpyrylium salts and electron rich bispyran from oxidative coupling of ferrocenylpyran. Example of redox systems switched by proton transfer
  作者：Fatou Ba、Nolwenn Cabon、Pascal Le Poul、Samia Kahlal、Jean-Yves Saillard、Nicolas Le Poul、Stéphane Golhen、Bertrand Caro、Françoise Robin-Le Guen

  DOI：10.1039/c3nj41126e

  日期：——

  Electro or chemical oxidation of ferrocenylmethylenepyran gave an ethanediferrocenylbispyrylium salt through the dimerization of a ferrocenylpyran radical-cation (C–C bond making). Electro or chemical reduction gave back the ferrocenylmethylenepyran (C–C bond breaking). This electrochemical reverse system constitutes an example of C–C bond making–breaking process in a metallocenyl series with rather high stability. DFT calculations and electrochemical studies were carried out in order to determine the electronic structure of the radical cation intermediate, the role of the ferrocenyl groups and the mechanism of the C–C bond making and C–C bond breaking processes. Reversible deprotonation of the ethanediferrocenylbispyrylium salt afforded an extended diferrocenylbismethylenepyran, which was subsequently reversibly oxidized to an ethenediferrocenylbispyrylium salt. X-Ray crystallographic data of diferrocenylbismethylenepyran and ethenediferrocenylbispyrylium salt allowed to determine the molecular movements, which come with the electron transfer (ET). A comparison with the behavior of the corresponding isoelectronic bisdithiafulvenes (extended TTF) and bisdithiolium salts was made.

  二茂铁基亚甲基吡喃的电氧化或化学氧化，通过二茂铁基吡喃自由基阳离子的二聚化（C-C 键生成），生成乙烷二茂铁基双吡喃盐。电还原或化学还原又产生了二茂铁基亚甲基吡喃（C-C 键断裂）。这种电化学反向体系是具有相当高稳定性的茂金属系列中 C-C 键生成-断裂过程的一个实例。为了确定自由基阳离子中间体的电子结构、二茂铁基团的作用以及 C-C 键生成和 C-C 键断裂过程的机理，我们进行了 DFT 计算和电化学研究。乙二基二茂铁双吡喃鎓盐的可逆去质子化反应产生了扩展的二茂铁双甲基吡喃，随后它被可逆氧化成乙二基二茂铁双吡喃鎓盐。通过二茂铁基双甲基吡喃和乙烯二茂铁基双吡喃盐的 X 射线晶体学数据，可以确定电子转移 (ET) 带来的分子运动。与相应的等电子双二硫富烯（扩展 TTF）和双二硫鎓盐的行为进行了比较。
• Ferrocenyl and pyridyl methylenepyrans as potential precursors of organometallic electron-rich extended bipyrans: Synthesis, characterization and crystal structure
  作者：Fatou Ba、Francoise Robin-Le Guen、Nolwenn Cabon、Pascal Le Poul、Stéphane Golhen、Nicolas Le Poul、Bertrand Caro

  DOI：10.1016/j.jorganchem.2009.10.006

  日期：2010.1

  Ferrocenyl and pyridyl methylenepyrans were obtained from a Wittig reaction between a pyran phosphorane and ferrocenyl or pyridyl-aldehydes. The nucleophilic nature of the exocyclic C-C bond allowed the formylation of these compounds by a Vilsmeier type reaction. All the new products were characterized by IR spectroscopy, H-1 and C-13 NMR spectroscopy, mass spectroscopy and (or) elemental analysis. Electrochemistry of representative compounds 2, 10 and 13 was undertaken.In addition, a crystal structure of the ferrocenylpyranylidene aldehyde 5 was described, and the pyrylium character of this compound was specified. (C) 2009 Elsevier B.V. All rights reserved.