1,1'-bis(N-tert-butylcarbamoyl)ferrocene | 181187-62-2

• 英文名称: 1,1'-bis(N-tert-butylcarbamoyl)ferrocene
• CAS: 181187-62-2
• 化学式: C₂₀H₂₈FeN₂O₂
• 分子量: 384.302
• InChiKey: MYFJXYLHDGRPOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  di-fluorocarbonylferrocene 、 叔丁胺 在 Me₂PrN 作用下， 以 二氯甲烷 为溶剂， 以74%的产率得到1,1'-bis(N-tert-butylcarbamoyl)ferrocene
  参考文献：
  名称：

  Ferrocene Encapsulated within Symmetric Dendrimers:  A Deeper Understanding of Dendritic Effects on Redox Potential

  摘要：

  Ferrocene has been encapsulated within a symmetric ether-amide dendritic shell and its redox potential monitored in a variety of solvents. The dendritic effect generated by the branched shell is different in different solvents. In less polar, non hydrogen bond donor solvents, attachment of the branched shell to ferrocene increases its E-1/2, indicating that oxidation to ferrocenium (charge buildup) becomes thermodynamically hindered by the dendrimer, a result explained by the dendrimer providing a less polar medium than that of the surrounding electrolyte solution. The effect of electrolyte concentration on redox potential was also investigated, and it was shown that the concentration of "innocent" electrolyte has a significant effect on the redox potential by increasing the overall polarity of the surrounding medium. Dendritic destabilization of charge buildup is in agreement with the majority of reported dendritic effects. A notable exception to this is provided by the asymmetric ferrocene dendrimers previously reported by Kaifer and co-workers, in which the branching facilitated oxidation, and it is proposed that in this case the dendritic effect is generated by a different mechanism. Interestingly, in methanol, the new symmetric ferrocene dendrimer exhibited almost no dendritic effect, a result explained by the ability of methanol to interact extensively with the branched shell, generating a more open superstructure. By comparison of all the new data with other reports, this study provides a key insight into the structure-activity relationships which control redox processes in dendrimers and also an insight into the electrochemical process itself.

  DOI：

  10.1021/ja0117478

文献信息

• The Isocyanate Route to Cyclopentadienyl-Carboxamide- and Cyclopentadienyl-Amino Ester-Substituted Metallocene Complexes
  作者：Markus Oberhoff、Lothar Duda、Jörn Karl、Roland Mohr、Gerhard Erker、Roland Fröhlich、Matthias Grehl

  DOI：10.1021/om960234k

  日期：1996.9.17

  Lithium cyclopentadienide adds to a variety of isocyanates [R-N=C=O, R = tert-butyl (a), n-butyl (b), cyclohexyl (c), phenyl (d), 3-pyridyl (e), 2-tetrahydropyranyl (f), adamantyl (g)] to yield the monocarbamoyl-substituted cyclopentadienides C(5)H(4)CONHR(-) 3 admired with varying amounts of the respective 1,2-dicarbamoyl-substituted C5H3(CONHR)(2)(-) systems 4 and a corresponding quantity of the C5H5- Starting material. Subsequent treatment of these reaction mixtures with anhydrous FeCl2 gave the 1,1'-dicarbamoylferrocenes 6 and the corresponding monocarbamoylferrocenes 5, which were easily separated by chromatography. The carbamoylferrocenes 5b, 5c, and 6d were characterized by X-ray crystal structure analyses. The (N-phenyl- and (N-adamantylcarbamoyl)cyclopentadienides were treated with CpTiCl(3) to give the carboxamide-substituted titanocene dichloride complexes [CP(C(5)H(4)CONHR)TiCl2] 8a (R = Ph) and Sh (R = adamantyl), respectively. Complex 8b was also characterized by X-ray diffraction. The valine ester-derived isocyanate reacts with lithium cyclopentadienide to give the N-valinyl-substituted carbamoylcyclopentadienide 3h. Subsequent treatment with FeCl2 or FeCl2/CpLi, respectively, produces the 1,1'-difunctionalized ferrocene 6h or the monofunctionalized ferrocene 5h. Both complexes were characterized by X-ray crystal structure analyses.