Kinetics of the ligand exchange reaction between tetrakis(acetylacetonato)-thorium(IV) and free acetylacetone in CD3CN and CDCl3.
Kinetics of the ligand exchange reaction between tetrakis(acetylacetonato)-thorium(IV) and free acetylacetone in CD3CN and CDCl3.
复制标题
CD3CN 和 CDCl3 中四乙酰丙酮钍 (IV) 与游离乙酰丙酮之间的配体交换反应动力学。
DOI：
10.1246/bcsj.57.1576
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发表时间：
1984
影响因子：
4
通讯作者：
H. Fukutomi
中科院分区：
文献类型：
--
作者：
Naoshi Fujiwara;H. Tomiyasu;H. Fukutomi
用1HNMR研究了四乙酰丙酮合钍（IV）与游离乙酰丙酮在CD3CN和CDCl3中的配体交换反应动力学。速率定律表示为rate =k[Th（acac）4][Hacac]enol，其中在0 °C下，CD3CN中的k=（1.0±0.1）×102 s−1 mol−1 kg，在−16 °C下，CDCl3中的k =（1.7±0.1）×102 s−1 mol−1 kg。碱的加入可使反应速率减慢，其减慢效应与碱的供体数密切相关。在所研究的条件下，活化熵给出了大的负值。提出了通过九配位中间体的配体交换机制来解释动力学规律。
Kinetics of the ligand exchange reaction between tetrakis(acetylacetonato)thorium(IV) and free acetylacetone in CD3CN and CDCl3 was studied by 1H NMR. The rate law was written as rate =k[Th(acac)4][Hacac]enol, where k=(1.0±0.1)×102 s−1 mol−1 kg at 0 °C in CD3CN and (1.7±0.1)×102 s−1 mol−1 kg at −16 °C in CDCl3. The rates were retarded by addition of bases and the retardation effect well correlated with the donor number of the bases. Under the conditions studied, the activation entropies gave large negative values. A ligand exchange mechanism passing through a nine-coordinate intermediate is proposed to interpret the kinetic law.