Actinyl Peroxide 二聚体 [An2O6]2+ 和 [(An2O6)(12-crown-4 ether)2]2+ (An = U、Np 和 Pu) 中的电子结构和异常化学键合,Inorganic Chemistry

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Actinyl Peroxide 二聚体 [An2O6]2+ 和 [(An2O6)(12-crown-4 ether)2]2+ (An = U、Np 和 Pu) 中的电子结构和异常化学键合
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-09-16 , DOI: 10.1021/acs.inorgchem.2c02399
Shu-Xian Hu _{1,

2} , Xiao-Xia You ₁ , Wen-Li Zou ₃ , Erli Lu ₄ , Xiang Gao ₂ , Ping Zhang _{2,

5}

Affiliation

众所周知，锕系过氧化物在锕系元素的环境迁移中发挥着重要作用，在核工业应用中具有重要的战略意义。与研究最多的过氧化铀相比，超铀对应物的研究仍然很少，需要更多关于这些物种的信息。在这项工作中，利用密度泛函理论和多参考波函数方法研究和分析了受实验启发的过氧化光炔二聚体（[An ₂ O ₆ ] ^{2+ 、An = U、Np 和 Pu）。}本研究确定这三种[An ₂ O ₆ ] ²⁺具有独特的电子结构和氧化态，如[(U ^VI O ₂ )₂ (O ₂ ) ^2– ] ²⁺ , [(Np ^VII O ₂ ) ₂ (O ^2– ) ₂ ] ²⁺和混合价 [(Pu ^VI/V O ₂ ) ₂ (O ₂ ) ^1– ] ²⁺。这项研究证明了两个桥连氧代配体在离子导向actinyl中的重要性，最多有四个电子空穴可用性，并导致[(Pu ^VI/V O ₂ ) ₂ (O ₂ ) ^1– ] ^{2+中不寻常的多自由基键合}. 此外，预测了热力学稳定的 12-冠 4 醚 (12C4) 螯合 [(An ₂ O ₆ )(12C4) ₂ ] ²⁺配合物，可以保持 [An ₂ O ₆ ] ²⁺的这些独特的电子结构, 其中 An ← O _12C4配位键合显示 12C4 结合能力从 κ ⁴ (U) 到 κ ³ (Np) 和 κ ⁴ (Pu) 的趋势。该研究揭示了过氧化物配合物中一系列早期锕系元素的有趣电子特性和键合特征，可以为含 An 物种的内在稳定性提供见解。

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Electronic Structures and Unusual Chemical Bonding in Actinyl Peroxide Dimers [An2O6]2+ and [(An2O6)(12-crown-4 ether)2]2+ (An = U, Np, and Pu)

As known, actinyl peroxides play important roles in environmental transport of actinides, and they have strategic importance in the application of nuclear industry. Compared to the most studied uranyl peroxides, the studies of transuranic counterparts are still few, and more information about these species is needed. In this work, experimentally inspired actinyl peroxide dimers ([An₂O₆]²⁺, An = U, Np, and Pu) have been studied and analyzed by using density functional theory and multireference wave function methods. This study determines that the three [An₂O₆]²⁺ have unique electronic structures and oxidation states, as [(U^VIO₂)₂(O₂)^2–]²⁺, [(Np^VIIO₂)₂(O^2–)₂]²⁺, and mixed-valent [(Pu^VI/VO₂)₂(O₂)^1–]²⁺. This study demonstrates the significance of two bridging oxo ligands with at most four electron holes availability in ionically directing actinyl and resulting in the unusual multiradical bonding in [(Pu^VI/VO₂)₂(O₂)^1–]²⁺. In addition, thermodynamically stable 12-crown-4 ether (12C4) chelated [(An₂O₆)(12C4)₂]²⁺ complexes have been predicted, that could maintain these unique electronic structures of [An₂O₆]²⁺, where the An ← O_12C4 dative bonding shows a trend in binding capacity of 12C4 from κ⁴ (U) to κ³ (Np) and κ⁴ (Pu). This study reveals the interesting electronic character and bonding feature of a series of early actinide elements in peroxide complexes, which can provide insights into the intrinsic stability of An-containing species.

更新日期：2022-09-16

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