Dynamic NMR as a nondestructive method for the determination of rates of dissociation. XII. Dissociation of the olefin in trans-dichloro(4-methyl-1-pentene)(4-substituted pyridine 1-oxide)platinum(II) complexes.
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概要
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The rates of dissociation of the olefin in the title compounds were determined by the dynamic NMR technique by taking advantage of the line shape change due to the isopropyl-methyl protons. The rates of dissociation were independent of concentration in bromoform-<I>d</I> solutions. The free energy of activation was between 17.0 and 19.1 kcal mol<SUP>−1</SUP> at 353 K for the compounds, of which line shapes were fully analyzed, depending upon the substituent in the pyridine ring and electron-withdrawing substituents giving low activation energy. The solvent effect was noticed on the dissociation rates: Aromatic hydrocarbons give higher rates of dissociation than halogenated hydrocarbons. Although solvents of strong affinity toward platinum(II) tend to decompose the complex, tetrahydrofuran-<I>d</I><SUB>8</SUB> was found to give definitely higher rates of dissociation of the olefin in <I>trans</I>-dichloro(4-methoxycarbonylpyridine 1-oxide)(3-methyl-1-butene)platinum(II) than bromoform-<I>d</I>, when it was used as a solvent. The mechanism of dissociation was discussed from the available data.
- 公益社団法人 日本化学会の論文
著者
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Oki Michinori
Department Of Chemistry Faculty Of Science Okawama University Of Science
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Toyota Shinji
Department Of Chemistry Faculty Of Science Okawama University Of Science
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Toyota Shinji
Department of Chemistry, Faculty o f Science, The University of Tokyo
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