DFT Studies of Uranyl Acetate, Carbonate, and Malonate, Complexes in Solution

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• 作者：Jordi V&aacute ; zquez ; Carles Bo ; Josep Maria Poblet ; Joan de Pablo ; and Jordi Bruno
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：September 22, 2003
• 年：2003
• 卷：42
• 期：19
• 页码：6136 - 6141
• 全文大小：116K
• 年卷期：v.42,no.19(September 22, 2003)
• ISSN：1520-510X

文摘

The aim of this work is to demonstrate that theoretical chemistry can be used as a complementary tool in determininggeometric parameters of a number of uranyl complexes in solution, which are not observable by experimentalmethods. In addition, we propose plausible structures with partial geometric data from experimental results. Agradient corrected DFT methodology with relativistic effects is used employing a COSMO solvation model. Thetheoretical calculations show good agreement with experimental X-ray and EXAFS data for the triacetato-dioxo-uranium(VI) and tricarbonato-dioxo-uranium(VI) complexes and are used to assign possible geometries for dicalcium-tricarbonato-dioxo-uranium(VI) and malonato-dioxo-uranium(VI) complexes. The results of this exercise indicatethat carbonate bonding in these complexes is mainly bidentate and that hydroxo bridging plays a critical role in thestabilization of the polynuclear uranyl complexes.