Deuterium isotope effect on the rate of ligand exchange between tetrakis(acetylacetonato)thorium(IV) and free acetylacetone in CD3CN.
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概要
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A deuterium isotope effect on the rate of acetylacetonate exchange between tetrakis(acetylacetonato)thorium(IV), Th(acac)<SUB>4</SUB>, and free acetylacetone in CD<SUB>3</SUB>CN has been examined by means of <SUP>1</SUP>H NMR technique. The second-order rate constant, <I>k</I>, which is expressed as a function of the observed first-order rate constant, <I>k</I><SUB>obsd</SUB>, and the concentration of acetylacetone in the enol form, [acetylacetone]<SUB>enol</SUB>, by <I>k</I>=<I>k</I><SUB>obsd</SUB>/[acetylacetone]<SUB>enol</SUB> was determined for the reaction of deuterated acetylacetone, Dacac, as well as undeuterated acetylacetone, Hacac. The ratio of second-order rate constants for Hacac and Dacac, <I>k</I><SUB>H</SUB>⁄<I>k</I><SUB>D</SUB>, was approximately 9. This large deuterium isotope effect strongly supports a mechanism proposed in a previous paper that the proton transfer process is the rate determining step of the whole reaction.
- 公益社団法人 日本化学会の論文
著者
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TOMIYASU Hiroshi
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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Tomiyasu Hiroshi
Research Laboratory For Nuclear Reactors Tokyo Institute Of Technology
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Fukutomi Hiroshi
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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Fujiwara Naoshi
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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Nakagawa Tomoe
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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TOMIYASU Hiroshi
Research Laboratory for Nuclear Reactor, Tokyo Institute of Technology
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