The Mechanism of Photo-substitution of Ferrocene in Haloalkane–Ethanol Solutions
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概要
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The mechanism of photo-substitution of ferrocene in haloalkane–ethanol solutions was investigated by the flash photolysis technique and other chemical methods mainly on the ferrocene–carbon tetrachloride–ethanol system. The photoreaction is initiated by the excitation of charge transfer state (electron transfer from ferrocene to carbon tetrachloride). In the absence of ethanol, CT-excitation leads to the decomposition of ferrocene to FeCl<SUB>3</SUB> with first order reaction kinetics of <I>k</I>=(1.6±0.5)×10<SUP>5</SUP> s<SUP>−1</SUP>. The formation of FeCl<SUB>3</SUB> was inhibited by ethanol effectively to give ethyl ferrocenecarboxylate. Diethylamine quenched the formation of FeCl<SUB>3</SUB>, whereas dimethyl sulfoxide, a stronger base than ethanol, is a less effective quencher than ethanol. These facts suggest that the most important role of ethanol is to ethanolyse trichloromethylferrocene, which otherwise decomposes to FeCl<SUB>3</SUB>.
- 公益社団法人 日本化学会の論文
著者
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Sugimori Akira
Department Of Chemistry Faculty Of Science And Technology Sophia University
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Akiyama Takeo
Department Of Chemistry Faculty Of Science And Technology Sophia University
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Hermann Horst
Max Planck-Institut für Kohlenforschung
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