Spectrophotometric study on the complex formation of hydroperoxide with tetraphenylporphyrin cobalt(II).
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概要
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The rate constants, activation energies, activation entropies and equilibrium constants for the coordination of 1,2,3,4-tetrahydro-1-naphthyl hydroperoxide (THP), 1-methyl-1-phenylethyl hydroperoxide (CHP) and <I>t</I>-butyl hydroperoxide (BHP) to para-substituted tetraphenylporphyrin Co(II), Co(<I>p</I>-X)TPP (X=OCH<SUB>3</SUB>, H, Cl) were obtained by the visible spectral method at 235–245 K. The rate constants of coordination were <I>k</I>=0.097–2.03×10<SUP>2</SUP> M<SUP>−1</SUP> s<SUP>−1</SUP>, the equilibrium constants being <I>K</I>=0.692–2.5×10<SUP>−6</SUP> M<SUP>−1</SUP>. As a <I>para</I>-substituent effect on <I>k</I> and <I>K</I>, the constants were found to increase with increase in the electron donating property of the substituent group. They also depend on the kind of hydroperoxide, the rate constants decreasing in the order <I>k</I><SUB>THP</SUB>><I>k</I><SUB>CHP</SUB>><I>k</I><SUB>BKP</SUB>, and the equilibrium constants in the order <I>K</I><SUB>CHP</SUB>><I>K</I><SUB>BHP</SUB>><I>K</I><SUB>THP</SUB>. Activation energies were 7.0—7.8 kcal mol<SUP>−1</SUP> and activation entropies −21–−25 cal K<SUP>−1</SUP>. No spectral change by the addition of hydroperoxide to CuTPP and NiTPP was observed.
- 公益社団法人 日本化学会の論文
著者
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Kamiya Yoshio
Department of Applied Chemistry Faculty of Engineering The University of Tokyo
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Yamada Teruaki
Department of Chemistry, Faculty of Science, Hokkaido University
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