Solution coordination chemistry of actinides: Thermodynamics, structure and reaction mechanisms
Solution coordination chemistry of actinides: Thermodynamics, structure and reaction mechanisms
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DOI：
10.1016/j.ccr.2005.10.005
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发表时间：
2006-04
影响因子：
20.6
通讯作者：
Z. Szabó;T. Toraishi;V. Vallet;I. Grenthe
中科院分区：
文献类型：
--
作者：
Z. Szabó;T. Toraishi;V. Vallet;I. Grenthe
本文的重点是实验和理论相结合的方法来获得微观信息的化学锕系元素在水溶液中。简要讨论了一些重要的实验方法，提供信息的平衡常数和构成的锕系元素配合物在溶液中，它们的结构和配体取代反应的速率和机制。微观的角度是通过比较实验数据与那些使用量子化学方法获得的;这里的重点是结构和反应机制。大多数实验数据涉及铀、钍和铥的化学性质，但这些信息可以推广到其他锕系元素，因为它们的化学性质在给定的氧化态下通常非常相似。溶液中络合物形成分析的第一步是基于平衡分析方法;这里讨论的重点是那些需要大量锕系元素的方法，因为这些方法在获得结构（大角度X射线散射，扩展X射线吸收光谱和NMR）和动态（NMR，弛豫和停流方法）信息中是必要的。最后，一些评论是如何的分子之间的复杂的形成UO 22+和小配体的理解可能是重要的天然存在的配体，如腐殖酸和富里酸和生物分子，如氨基酸，蛋白质和核苷酸。
The emphasis of this review is on the combination of experimental and theoretical methods to obtain microscopic information on the chemistry of actinides in aqueous solution. A brief discussion is given of some important experimental methods that provide information on the equilibrium constants and constitution of actinide complexes in solution, their structure and the rate and mechanism of ligand substitution reactions. The microscopic perspective is provided by a comparison of experimental data with those obtained using quantum chemical methods; the emphasis is here on structure and reaction mechanisms. Most of the experimental data refer to the chemistry of uranium, thorium and curium, but this information can be generalized to other actinides as their chemistry is often very similar in a given oxidation state. The first step in the analysis of complex formation in solution is based on equilibrium analytical methods; the discussion is here focused on those requiring macro amounts of actinides, as these are necessary in the methods used to obtain structure (large angle X-ray scattering, extended X-ray absorption spectroscopy and NMR) and dynamic (NMR, relaxation and stopped-flow methods) information. Finally, some comments are made on how the molecular understanding of complex formation between UO22+and small ligands may be of importance in naturally occurring ligands like humic and fulvic acids and biomolecules, such as amino acids, proteins and nucleotides.