Kinetics of the ligand-exchange reactions in Th(tta)4 and Th(tta)4dmso in organic solvents.
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概要
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The exchange reactions of 2-thenoyltrifluoroacetonate (tta) in Th(tta)<SUB>4</SUB> and of dimethyl sulfoxide (dmso) in Th(tta)<SUB>4</SUB>dmso have been studied by the NMR method. It was found that the first-order rate constant of tta exchange in acetonitrile-<I>d</I><SUB>3</SUB> depended linearly on the concentrations of Htta in the enol form, Htta<SUB>enol</SUB>, and that the rate was retarded markedly by the addition of DMSO. The activation parameters Δ<I>H</I><SUP>\neweq</SUP> (kJ mol<SUP>−1</SUP>) and Δ<I>S</I><SUP>\neweq</SUP> (JK<SUP>−1</SUP> mol<SUP>−1</SUP>) were determined to be 43.9±0.5 and −58.4±1.5, respectively and the mechanism including the formation of a nine-coordinate intermediate was proposed. For Th(tta)<SUB>4</SUB>dmso, the rate of dmso exchange in acetone-<I>d</I><SUB>6</SUB> was much faster than that of β-diketonate exchange, and an interchange mechanism was proposed on the basis of a nonlinear dependency of the first-order rate constant on the free DMSO concentration.
- 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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Fujiwara Naoshi
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology
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