科研之友
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摘要
Ferrocenes with up to four formyl functionalities have been synthesized by selective one-or two-fold ortho-lithiation of 1,1'-di(1,3-dioxan-2-yl)ferrocene followed by the reaction with dimethylformamide. Subsequent deprotection afforded tri- and tetraformyl-ferrocene in good yields. Wittig reactions convert the aldehydes to tri-and tetravinyl-ferrocene. The structures of three formyl-ferrocenes in the solid-state have been determined by single crystal X-ray diffraction. In two of the structures the ferrocene moieties form 1D chains by parallel displaced p-interactions with Cp center dot center dot center dot Cp distances as short as 3.21 angstrom. Electrochemical measurements (CV) demonstrated an irreversible behavior of the electron-poor multi-formyl ferrocenes. Reducing the measurement temperature down to -40 degrees C and the usage of [(NBu4)-Bu-n][B(C6F5)(4)] prevents side reactions and hence reversible redox-processes could be obtained. It was found that the number of formyl functionalities correlates with the ferrocenyl's redox potential in a strictly linear fashion.
- 出版日期2016-2-15
