3-ferrocenyl-1,2,4,5,6,7-hexamethylindene | 959855-73-3

• 英文名称: 3-ferrocenyl-1,2,4,5,6,7-hexamethylindene
• CAS: 959855-73-3
• 化学式: C₂₅H₂₈Fe
• 分子量: 384.344
• InChiKey: DNTBEUHAHFNLGP-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：

  3-ferrocenyl-1,2,4,5,6,7-hexamethylindene 、 silver tetrafluoroborate 以 乙醚 为溶剂， 以36%的产率得到[(3-ferrocenyl-1,2,4,5,6,7-hexamethylindene(-e))]BF4
  参考文献：
  名称：

  Charge Transfer through Isomeric Unsaturated Hydrocarbons. Redox Switchable Optical Properties and Electronic Structure of Substituted Indenes with a Pendant Ferrocenyl

  摘要：

  A family of (ferrocenyl)indenes, (2-ferrocenyl)indene, (2-ferrocenyl)tetramethylindene, (2-ferrocenyl)hexamethylindene, (3-ferrocenyl)indene, and (3-ferrocenyl)hexamethylindene, and the corresponding monooxidized cations have been prepared. The results of a structural and spectroelectrochemical study are discussed. The availability of pairs of isomers with known geometries and differently methylated indenes allowed the detailed investigation of how slight geometric and electronic modifications affect their physical properties. The molecular structures have been determined by X-ray diffraction and compared with the fully optimized structures calculated with state-of-the-art DFT methods. Calculated and crystallographic structures agree in establishing the dependence of the orientation of the indene moiety and the ferrocenyl cyclopentadienyl rings on the degree of methylation. The UV-vis spectra and in particular the appearance upon oxidation of a new near-IR absorption, whose energy and intensity increase with the degree of methylation and cyclopentadienyl-indene planarity, are rationalized in the framework of the Hush theory and at quantum chemistry level by DFT and TD-DFT calculations.

  DOI：

  10.1021/om700673m
• 作为产物：
  描述：

  二茂铁 、 叔丁基锂 、 2,3,4,5,6,7-tetramethylindane-1-one 在 HCl 作用下， 以 正戊烷 为溶剂， 以37%的产率得到3-ferrocenyl-1,2,4,5,6,7-hexamethylindene
  参考文献：
  名称：

  Charge Transfer through Isomeric Unsaturated Hydrocarbons. Redox Switchable Optical Properties and Electronic Structure of Substituted Indenes with a Pendant Ferrocenyl

  摘要：

  A family of (ferrocenyl)indenes, (2-ferrocenyl)indene, (2-ferrocenyl)tetramethylindene, (2-ferrocenyl)hexamethylindene, (3-ferrocenyl)indene, and (3-ferrocenyl)hexamethylindene, and the corresponding monooxidized cations have been prepared. The results of a structural and spectroelectrochemical study are discussed. The availability of pairs of isomers with known geometries and differently methylated indenes allowed the detailed investigation of how slight geometric and electronic modifications affect their physical properties. The molecular structures have been determined by X-ray diffraction and compared with the fully optimized structures calculated with state-of-the-art DFT methods. Calculated and crystallographic structures agree in establishing the dependence of the orientation of the indene moiety and the ferrocenyl cyclopentadienyl rings on the degree of methylation. The UV-vis spectra and in particular the appearance upon oxidation of a new near-IR absorption, whose energy and intensity increase with the degree of methylation and cyclopentadienyl-indene planarity, are rationalized in the framework of the Hush theory and at quantum chemistry level by DFT and TD-DFT calculations.

  DOI：

  10.1021/om700673m

文献信息

• Tunable electronic coupling in iron–chromium mixed-valence ions of methylated Cp-indene ligands
  作者：Saverio Santi、Laura Orian、Alessandro Donoli、Christian Durante、Annalisa Bisello、Marilena Di Valentin、Paolo Ganis、Franco Benetollo、Alberto Ceccon

  DOI：10.1016/j.jorganchem.2008.09.024

  日期：2008.12

  2-(ferrocenyl)indene, and the degree of indene methylation (tetramethyl- and hexamethyl-) have been prepared and studied with the aim to stabilise the mono- and dications generated by chemical and electrochemical oxidation, and at same time to tune the metal–metal electronic coupling in the mixed-valence cations. The magnitude of electronic delocalisation and spin density in the cations have been monitored by

  一系列的异η的6 - [（二茂铁基）茚] -Cr（CO）3制备并研究了二茂铁基，1-（二茂铁基）茚和2-（二茂铁基）茚以及茚甲基化程度（四甲基和六甲基-）不同的配合物，目的是稳定单-化学和电化学氧化产生的阳离子，同时调整混合价阳离子中的金属-金属电子耦合。阳离子中电子离域的大小和自旋密度已通过光学技术（紫外可见，近红外，中红外）和EPR光谱法进行了监测。在Marcus-Hush理论的框架内以及在DFT和TD-DFT方法的量子化学水平上对结果进行了合理化，证明了金属与金属之间的电子耦合发生的程度取决于茚甲基化的程度。