Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO_2~(2+) and PuO_2~(2+)in Comparison with UO_2~(2+)

Chao Xu; Guoxin Tian; Simon J. Teat; Guokui Liu; Linfeng Rao

首页> 外文期刊>Chemistry: A European journal >Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO_2~(2+) and PuO_2~(2+)in Comparison with UO_2~(2+)

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Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO_2~(2+) and PuO_2~(2+)in Comparison with UO_2~(2+)

机译：六价Act基阳离子的热力学和结构趋势：与NPO_2〜（2+）比较，二吡啶甲酸与NpO_2〜（2+）和PuO_2〜（2+）的络合

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The complexation of NpO_2~(2+) and PuO_2~(2+) with dipicolinic acid (DPA) has been investigated in 0.1m NaClO4 by spectrophotometry, microcalorimetry, and single crystal diffractometry. Formation of 1:1 and 1:2 (metal/ligand molar ratio) complexes of DPA with NpO_2~(2+) and PuO_2~(2+) were identified and the thermodynamic parameters were determined and compared with those of UO_2~(2+). All three hexavalent actinyl cations form strong 1:1 DPA complexes with slightly decreasing but comparable stability constants from UO_2~(2+) to PuO_2~(2+), whereas the stability constants of the 1:2 complexes (logb2) decrease substantially along the series (16.3 for UO_2L_2~(2-), 15.17 for NpO_2L_2~(2-), and 14.17 for PuO_2L_2~(2-) at 25 8C). The enthalpies of complexation for the 1:2 complexes become less exothermic from UO_2L_2~(2-) (-28.9 kJmol~(-1)), through NpO_2L_2~(2-) (-27.2 kJmol~(-1)), and to PuO_2L_2~(2-) (-22.7 kJmol~(-1)). The trends in the thermodynamic parameters are discussed in terms of the effective charge of the cations and the steric constraints in the structures of the complexes. In addition, the features of the absorption spectra, including the wavelength and intensity of the absorption bands, are related to the perturbation of the ligand field and the symmetry of the actinyl complexes.

机译：通过分光光度法，微量量热法和单晶衍射法研究了NpO_2〜（2+）和PuO_2〜（2+）与二吡啶甲酸（DPA）的络合物。鉴定了DPA与NpO_2〜（2+）和PuO_2〜（2+）形成1：1和1：2（金属/配体摩尔比）的配合物，并确定了热力学参数并将其与UO_2〜（2 +）。所有三个六价act基阳离子均形成强1：1 DPA配合物，从UO_2〜（2+）到PuO_2〜（2+）的稳定常数略有降低，但可比，但1：2配合物（logb2）的稳定常数随该序列（在25 8C下，UO_2L_2〜（2-）为16.3，NpO_2L_2〜（2-）为15.17，PuO_2L_2〜（2-）为14.17）。 1：2配合物的络合焓从UO_2L_2〜（2-）（-28.9 kJmol〜（-1））到NpO_2L_2〜（2-）（-27.2 kJmol〜（-1））放热变小到PuO_2L_2〜（2-）（-22.7 kJmol〜（-1））。根据阳离子的有效电荷和配合物结构中的空间约束，讨论了热力学参数的趋势。另外，吸收光谱的特征，包括吸收带的波长和强度，与配体场的扰动和the基配合物的对称性有关。

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《Chemistry: A European journal》 |2013年第49期|共9页
作者
Chao Xu; Guoxin Tian; Simon J. Teat; Guokui Liu; Linfeng Rao;
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actinides; coordination modes; structure elucidation; thermodynamics;

机译：in系元素;配位模式;结构阐明;热力学;

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Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO_2~(2+) and PuO_2~(2+)in Comparison with UO_2~(2+)

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