Copper(I) Perchlorate Complexes of Allyl, 2-Methylallyl and <I>cis</I>-and <I>trans</I>-2-Butenyl Alcohols
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概要
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[Cu(allyl alcohol) (H<SUB>2</SUB>O)]ClO<SUB>4</SUB> (abb. Cu(all)(H<SUB>2</SUB>O)ClO<SUB>4</SUB>), [Cu(allyl alcohol)<SUB>2</SUB>(H<SUB>2</SUB>O)]ClO<SUB>4</SUB> (abb. Cu(all)<SUB>2</SUB>-(H<SUB>2</SUB>O)ClO<SUB>4</SUB>), [Cu(2-methylallylalcohol)(H<SUB>2</SUB>O)]ClO<SUB>4</SUB> (abb. Cu(meth)(H<SUB>2</SUB>O)ClO<SUB>4</SUB>) and [Cu(<I>cis</I>- and <I>trans</I>-2-butenyl alcohol)<SUB>2</SUB> (H<SUB>2</SUB>O)]ClO<SUB>4</SUB> (abb. Cu(<I>cis</I>-and <I>trans</I>- but<SUB>2</SUB> (H<SUB>2</SUB>O)ClO<SUB>4</SUB>) were synthesized. It was shown by means of equivalent conductance that Cu(all)(H<SUB>2</SUB>O)ClO<SUB>4</SUB> is a strong electrolyte of uni-uni valent in acetone. The molecular weight of Cu(all)(H<SUB>2</SUB>O)ClO<SUB>4</SUB> obtained from measurements of the direct vapor-pressure depression of acetone showed that the complex is monomeric. The C=C stretching band of the allylic alcohol shifts by about 100 cm<SUP>−1</SUP> to the lower frequency side upon coordination. The chemical shifts of the vinyl protons in these complexes shift by about 0.5–1 ppm to the higher frequency side than those of free alcohols. It was concluded that the allylic alcohol coordinates to the copper atom through both the double bond and the oxygen atom. The equilibrium constant corresponding to Cu(<I>trans</I>-but)<SUP>+</SUP><SUB>2</SUB>(H<SUB>2</SUB>O)ClO<SUB>4</SUB>+2<I>cis</I>-2-butenyl alcohol=Cu(<I>cis</I>-but)<SUP>+</SUP><SUB>2</SUB>(H<SUB>2</SUB>O)ClO<SUB>4</SUB>+2<I>trans</I>-2-butenyl alcohol in 2-butenyl alcohol was estimated to be 9.82 at 25°C and the enthalpy change was estimated to be −3.13kcal/mol.
- 公益社団法人 日本化学会の論文
著者
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OGURA Tetsuya
Departamento de Quìmica, CEN, Universidad Autónoma de Guadalajara Apdo
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Manabe Osamu
The Osaka Municipal Technical Research Institute
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Ishino Yoshio
Department of Chemistry, Faculty of Science, Osaka City University
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Noda Kenichiro
The Osaka Municipal Technical Research Institute
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Hirashima Tsuneaki
The Osaka Municipal Technical Research Institute
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