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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computational Study of Actinyl Ion Complexation with Dipyriamethyrin Macrocyclic Ligands
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Computational Study of Actinyl Ion Complexation with Dipyriamethyrin Macrocyclic Ligands

机译：用二吡替替替替替林蛋白致二硼丝酰氯配体的计算研究

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摘要

Relativistic density functional theory has been employed to characterize [AnO_(2)(L)]~(0/-1) complexes, where An = U, Np, Pu, and Am, and L is the recently reported hexa-aza porphyrin analogue, termed dipyriamethyrin, which contains six nitrogen donor atoms (four pyrrolic and two pyridine rings). Shorter axial (An═O) and longer equatorial (An–N) bond lengths are observed when going from An~(VI) to An~(V). The actinide to pyrrole nitrogen bonds are shorter as compared to the bonds to the pyridine nitrogens; the former also play a dominant role in the formation of the actinyl (VI and V) complexes. Natural population analysis shows that the pyrrole nitrogen atoms in all the complexes carry higher negative charges than the pyridine nitrogens. Upon binding actinyl ions with the ligand a significant ligand-to-metal charge transfer takes place in all the actinyl (VI and V) complexes. The formation energy of the actinyl(VI,V) complexes in the gas-phase is found to decrease in the order of UO_(2)L > PuO_(2)L > NpO_(2)L > AmO_(2)L. This trend is consistent with results for the formation of complexes in dichloromethane solution. The calculated ΔG and ΔH values are negative for all the complexes. Energy decomposition analysis (EDA) indicates that the interactions between actinyl(V/VI) and ligand are mainly controlled by electrostatic components over covalent orbital interactions, and the covalent character gradually decreases from U to Am for both pentavalent and hexavalent actinyl complexes.
机译：利用相对论密度泛函理论对[AnO_2（L）]~（0/-1）配合物进行了表征，其中An=U、Np、Pu和Am，L是最近报道的六氮杂卟啉类似物，称为联吡啶亚甲基吡啶，它包含六个氮施主原子（四个吡咯环和两个吡啶环）。短轴（An）═O） 当从An~（VI）到An~（V）时，观察到更长的赤道（An-N）键长度。锕系到吡咯氮键比吡啶氮键短；前者在锕基（VI和V）络合物的形成中也起主导作用。自然布居分析表明，所有配合物中的吡咯氮原子比吡啶氮原子带更高的负电荷。当锕基离子与配体结合时，所有锕基（VI和V）络合物中都发生了重要的配体-金属电荷转移。发现锕基（VI，V）配合物在气相中的形成能按UO_2）L>PuO_2）L>NpO_2）L>AmO_2）L的顺序降低。这一趋势与二氯甲烷溶液中形成配合物的结果一致。所有配合物的计算ΔG和ΔH值均为负值。能量分解分析（EDA）表明，在共价轨道相互作用中，锕基（V/VI）和配体之间的相互作用主要由静电组分控制，五价和六价锕基配合物的共价性质从U逐渐降低到Am。

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