Reaction Kinetics of the Redox Decomposition of Hydroxymercurated Propylene in Aqueous Solution Followed by Time-Sequential NMR Spectroscopy
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概要
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The redox decomposition process of hydroxymercurated propylene in aqueous solution yielding acetone has been followed by time-sequential NMR spectroscopy <I>in situ</I>. No reaction intermediates and reaction products other than acetone were observed. Stoichiometric relationship holds between the reactant and the product during the reaction, which was verified by NMR spectra. The reaction rate was confirmed to be of first order with respect to mercurial. Although the rate was accelerated at higher acidity in solution, a similar rate enhancement took place by addition of neutral salts. At a certain ionic strength, no close linear correlation between the apparent rate constants and proton concentration was observed. In contrast, excellent linear dependence was obtained by the thermodynamic activities of the added electrolytes including acid. Since the apparent rate constant was independent of the concentration of free mercuric ion, a monomolecular mechanism is proposed. Taking into account the rate dependence upon added electrolytes, the redox decomposition of the hydroxymercurated olefins to give carbonyl compounds seems to proceed only when an aquo ligand is removed from the carbon-bonded mercuric ion.
- 公益社団法人 日本化学会の論文
著者
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Saito Yasukazu
Department Of Industrial Chemistry Faculty Of Engineering The University Of Tokyo
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Saito Yasukazu
Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo
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Matsuo Masashi
Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo
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