Kinetics of ligand-exchange reactions in tetrakis(acetylacetonato)uranium(IV) in organic solvents.
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概要
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The kinetics of ligand-exchange reactions between tetrakis(acetylacetonato)uranium(IV) [U(acac)<SUB>4</SUB>] (acac=acetylacetonate) and free acetylacetone Hacac in various organic solvents, CDCl<SUB>3</SUB>, C<SUB>6</SUB>D<SUB>6</SUB>, and CD<SUB>3</SUB>CN has been studied by <SUP>1</SUP>H NMR. The rate laws were found to change remarkably with these solvents used. The observed first-order rate constant <I>k</I><SUB>obsd</SUB> in CDCl<SUB>3</SUB> depended linearly on the concentration of free Hacac in the enol form as <I>k</I><SUB>obsd</SUB>=<I>k</I><SUB>s</SUB>[Hacac]<SUB>enol</SUB>, while the plots of <I>k</I><SUB>obsd</SUB> vs. [Hacac]<SUB>enol</SUB> in C<SUB>6</SUB>D<SUB>6</SUB> deviated from straight lines in higher concentrations of Hacac<SUB>enol</SUB>. The exchange rate was much slower in CD<SUB>3</SUB>CN than in CDCl<SUB>3</SUB> and C<SUB>6</SUB>D<SUB>6</SUB>, and <I>k</I><SUB>obsd</SUB> increased only slightly with [Hacac]<SUB>enol</SUB>. Addition of dimethyl sulfoxide (DMSO) in C<SUB>6</SUB>D<SUB>6</SUB> yielded the retardation of exchange rate giving a rate law <I>k</I><SUB>obsd</SUB><SUP>−1</SUP>=<I>p</I>+<I>q</I>[DMSO], where <I>p</I> and <I>q</I> are constants. From the results obtained in these solvents, a mechanism passing through nine-coordinate intermediates was proposed.
- 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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Fukutomi Hiroshi
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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Ohno Hideki
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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