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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Solvation Structures and Solvent Exchange Reactions of Metal Ions in Various Coordinating Solvents
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Solvation Structures and Solvent Exchange Reactions of Metal Ions in Various Coordinating Solvents

机译：各种配位溶剂中金属离子的溶剂化结构和溶剂交换反应

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摘要

The solvation structures and the reactin mechanisms of the solvent exchange reactions of metal ions are essential aspects of the interactions of the metal ions with the solvent molecules and information about them is necessary to under-stand the reactivities of the metal ions in solution. The solvation structures in various coordinating solvents were dis-cussed on the basis of the structure parameters determined by the extended X-ray absorption fine structure technique, referring to the ionic size, ionic charge, and electronic configuration of the metal ions and the bulkiness and electron donating ability of the solvent molecules. It was shown that the deficient bulkiness of 1,1,3,3-tetramethylurea leads to a unique variation in the solvation number for a series of 3d-block metal ions and that the strong electron donating bability of propylamine reduces the solvation number. The solvent exchange mechanisms of various metal ions were discussed on the basis of the activation parameters determined by the nuclear magnetic resonance technique, and the effects of the ionic charge, ionic size, and electronic configuration of the metal ions were regularized. The kinetic results for the solvent exchange of the Ni~(2+) and Mn~(2+) ions in a series of nitriles revealed the effect of the solvent bulkiness on the variation in the mechanism. The kinetic chelate effect was pointed out on the basis of the activation parameters for the solvent exchange of the divalent first-row transition metal ions in bidentate solvents such as ethylenediamine and trimethylenediamine.
机译：金属离子的溶剂交换反应的溶剂化结构和反应机理是金属离子与溶剂分子相互作用的重要方面，有关它们的信息对于理解溶液中金属离子的反应性是必需的。根据扩展的X射线吸收精细结构技术确定的结构参数，讨论了各种配位溶剂中的溶剂化结构，并参考了金属离子的离子尺寸，离子电荷和电子构型以及其蓬松度和溶剂分子的电子给电子能力。结果表明，不足的1,1,3,3-四甲基脲的膨松度导致一系列3d嵌段金属离子的溶剂化数发生独特变化，丙胺的强供电子能力降低了溶剂化数。根据核磁共振技术确定的活化参数，讨论了各种金属离子的溶剂交换机理，并规范了金属离子的电荷，离子尺寸和电子构型的影响。一系列腈中Ni〜（2+）和Mn〜（2+）离子交换溶剂的动力学结果揭示了溶剂体积对机理变化的影响。根据在二齿溶剂如乙二胺和三亚甲基二胺中二价第一行过渡金属离子进行溶剂交换的活化参数指出了动力学螯合作用。

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