有关含有第 10 族金属的杂多金属铀酰络合物的合成和氧化还原化学的观察结果

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of Chemical Research Pub Date : 2024-02-09 DOI:10.1515/ract-2023-0237
Emily R. Mikeska, Natalie M. Lind, Alexander C. Ervin, Celine Khalife, Joseph P. Karnes, James D. Blakemore
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引用次数: 0

摘要

文献报道表明,希夫碱配体可以作为合成含有过渡金属和铀酰二价(UO2 2+)的杂二金属络合物的可靠平台。然而,尽管锕系元素的氧化还原反应在核燃料后处理和分离研究中具有重要意义,但在合成含有第二排或第三排过渡金属的络合物或测量相应杂多金属络合物的氧化还原特性方面的工作还没有取得进展。在此,我们制备了含有相应第 10 族金属的金属配体(以[Ni]、[Pd]和[Pt]表示),并探索了获得含有铀酰离子(UO2 2+)的物种的合成策略,目的是了解次级金属如何调节以铀为中心的氧化还原化学。本文报告了双金属络合物 [Ni,UO2] 的合成和氧化还原特性,以及将所选合成策略扩展到与钯和铂的络合物的因素。对金属配体 [Pd] 和 [Pt] 进行 X 射线衍射分析所得到的红外和固态结构数据表明,这些配合物中的金属中心采用了预期的方形平面几何结构,而双金属 [Ni,UO2] 的结构则表明,铀酰分子会影响 Ni(II) 的配位环境,包括诱发配合物配体骨架的皱褶,在皱褶中,苯基环以伞形方式折叠在含镍核心周围。在 Ni(II) 和 Pd(II) 的杂双金属配合物上收集的循环伏安数据证明了以铀为中心的氧化还原循环,以及与 Ni(II) 或有机配体骨架有关的其他还原的可及性。总之,这些结果突出了多金属体系中可以观察到的独特氧化还原行为,以及有助于获得含有铀酰二阳离子的可调多金属复合物的设计理念。
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Observations regarding the synthesis and redox chemistry of heterobimetallic uranyl complexes containing Group 10 metals
Literature reports have demonstrated that Schiff-base-type ligands can serve as robust platforms for the synthesis of heterobimetallic complexes containing transition metals and the uranyl dication (UO2 2+). However, efforts have not advanced to include either synthesis of complexes containing second- or third-row transition metals or measurement of the redox properties of the corresponding heterobimetallic complexes, despite the significance of actinide redox in studies of nuclear fuel reprocessing and separations. Here, metalloligands denoted [Ni], [Pd], and [Pt] that contain the corresponding Group 10 metals have been prepared and a synthetic strategy to access species incorporating the uranyl ion (UO2 2+) has been explored, toward the goal of understanding how the secondary metals could tune uranium-centered redox chemistry. The synthesis and redox characterization of the bimetallic complex [Ni,UO2] was achieved, and factors that appear to govern extension of the chosen synthetic strategy to complexes with Pd and Pt are reported here. Infrared and solid-state structural data from X-ray diffraction analysis of the metalloligands [Pd] and [Pt] show that the metal centers in these complexes adopt the expected square planar geometries, while the structure of the bimetallic [Ni,UO2] reveals that the uranyl moiety influences the coordination environment of Ni(II), including inducement of a puckering of the ligand backbone of the complex in which the phenyl rings fold around the nickel-containing core in an umbrella-shaped fashion. Cyclic voltammetric data collected on the heterobimetallic complexes of both Ni(II) and Pd(II) provide evidence for uranium-centered redox cycling, as well as for the accessibility of other reductions that could be associated with Ni(II) or the organic ligand backbone. Taken together, these results highlight the unique redox behaviors that can be observed in multimetallic systems and design concepts that could be useful for accessing tunable multimetallic complexes containing the uranyl dication.
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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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