Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 1, 91058 Erlangen, Germany.
Department of Chemistry, Chair of Inorganic and Metal-Organic Chemistry, Technical University of Munich (TUM), TUM School of Natural Sciences, Lichtenbergstrasse 4, 85748 Garching, Germany.
Chem Rev. 2023 Jun 28;123(12):7761-7781. doi: 10.1021/acs.chemrev.2c00903. Epub 2023 May 3.
Uranium complexes can be stabilized in a wide range of oxidation states, ranging from U to U and a very recent example of a U complex. This review provides a comprehensive summary of electrochemistry data reported on uranium complexes in nonaqueous electrolyte, to serve as a clear point of reference for newly synthesized compounds, and to evaluate how different ligand environments influence experimentally observed electrochemical redox potentials. Data for over 200 uranium compounds are reported, together with a detailed discussion of trends observed across larger series of complexes in response to ligand field variations. In analogy to the traditional Lever parameter, we utilized the data to derive a new uranium-specific set of ligand field parameters (L) that more accurately represent metal-ligand bonding situations than previously existing transition metal derived parameters. Exemplarily, we demonstrate (L) parameters to be useful for the prediction of structure-reactivity correlations in order to activate specific substrate targets.
铀配合物可以稳定存在于很宽的氧化态范围内，从 U 到 U，并且最近还出现了一个 U 配合物的例子。本综述全面总结了非水电解质中报道的铀配合物的电化学数据，为新合成的化合物提供了明确的参考，并评估了不同配体环境如何影响实验观察到的电化学氧化还原电位。报告了超过 200 种铀化合物的数据，并详细讨论了针对较大系列配合物的响应配体场变化的观察到的趋势。类似于传统的勒弗参数，我们利用这些数据推导出了一套新的铀专用配体场参数（L），这些参数比以前基于过渡金属的参数更能准确地表示金属-配体键合情况。举例来说，我们证明（L）参数可用于预测结构-反应性相关性，以激活特定的底物靶标。
