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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Chemical Reactivity in AOT Microemulsions: Kinetics of Water Replacement in a Square-Planar Palladium(II) Aquo Complex by Monoalkylthioureas
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Chemical Reactivity in AOT Microemulsions: Kinetics of Water Replacement in a Square-Planar Palladium(II) Aquo Complex by Monoalkylthioureas

机译：AOT微乳中的化学反应性：单烷基硫脲在正方形平面钯（II）水络合物中水置换的动力学

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摘要

The kinetics of water replacement in the cationic palladium(II) aquo complex [Pd(Et↓(4)dien)(H↓(2)O)]↑（2+), where Et↓(4)dien = Et↓(2)N(CH↓(2))↓(2)NH(CH↓(2))↓(2)NEt↓(2), by thiourea, methylthiourea, and ethylthiourea have been studied at 25.0 ℃ in heptane-AOT-water microemulsion over a wide range of the molar ratio R (=[H↓(2)O]/[AOT]) at the constant surfactant concentration of 0.13 mol dm↑(-3). The reaction rates are significantly higher in micro-emulsions than in bulk water and decrease rapidly as the parameter R increases. The kinetic data, interpreted quantitatively by applying the pseudophase model to the microemulsion, indicate that there is a weak partitioning of the nucleophiles between the water core and the AOT interface, while the palladium complex is strongly associated with the negatively charged surfactant interface. All the substitution reactions take place only in the AOT interfacial region with rates very close to those in bulk water. The estimated partition coefficients of the nucleophiles increase with increasing their hydrophobic character. These data are discussed and compared with those previously obtained in the presence of cationic and anionic micelles.
机译：阳离子钯（II）水溶液络合物[Pd（Et↓（4）dien）（H↓（2）O）]↑（2+）中水的置换动力学，其中Et↓（4）dien = Et↓（ 2）N（CH↓（2））↓（2）NH（CH↓（2））↓（2）NEt↓（2）在25.0℃下于庚烷-AOT-中研究了硫脲，甲基硫脲和乙基硫脲在恒定的表面活性剂浓度为0.13 mol dm↑（-3）的摩尔比R（= [H↓（2）O] / [AOT]）的宽范围内制备水微乳液。在微乳液中，反应速率明显高于在本体水中，并且随着参数R的增加而迅速降低。通过将假相模型应用于微乳液进行定量解释的动力学数据表明，在水核与AOT界面之间亲核试剂的分配很弱，而钯配合物则与带负电荷的表面活性剂界面密切相关。所有取代反应仅发生在AOT界面区域，发生率与散装水中的发生率非常接近。亲核试剂的估计分配系数随其疏水特性的增加而增加。对这些数据进行了讨论，并与先前在阳离子和阴离子胶束存在下获得的数据进行了比较。

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