Probing Actinide Covalency using NMR Spectroscopy and DFT Calculations

研究领域：合成配位化学、计算和理论化学、分析科学。鳗系元素科学的中心目标是更好地量化鳗系元素-配体成键的共价性，并将其与元素周期表其余部分的元素联系起来。在实验上，探索吖系元素键的共价性是具有挑战性的；几乎没有共价性的实验测量方法。然而，有了新的分子，表现出隐藏在接近热力学下沉的简单系统中的特征，我们可以使用核磁共振光谱来实验地探测鳗的共价性。交警。2021，12，文章编号5649)，我们展示了可以使用15N核磁共振波谱(溶液和固态MAS)来探测铀-氮化物三键的共价性，揭示了前所未有的核磁共振波谱性质和鳗系元素的共价性。实验和计算方法的结合对这一成功是至关重要的。在这个项目中，您将准备一系列现有的和新的鳗系元素配合物，有时带有同位素标记，除了用通常的分析技术对它们进行表征外，还将通过详细的核磁共振和计算研究来探索关键鳗系元素-配体连接的共价性，以量化共价性。我们的总体目标是，通过对各种相关络合物和核磁共振核的研究，建立我们对鳗系元素共价性的理解。

AREAS: SYNTHETIC COORDINATION CHEMISTRY, COMPUTATIONAL AND THEORETICAL CHEMISTRY, ANALYTICAL SCIENCE A central aim of actinide science is to better quantify the covalency of actinide-ligand bonding, and to relate this to elements across the rest of the periodic table. Experimentally probing the covalency of actinide bonding is challenging; there are few experimental measures of covalency. Nevertheless, with novel molecules, that display traits which remain hidden in simple systems close to thermodynamic sinks, we can use NMR spectroscopy to probe actinide-covalency experimentally.Previously (Nat. Commun. 2021, 12, article number 5649), we showed that the covalency of a uranium-nitride triple bond could be probed using 15N NMR spectroscopy (solution and solid-state MAS), revealing unprecedented NMR spectroscopic properties and actinide covalency. The marriage of experimental and computational methods was essential to this success.In this project, you will prepare a range of existing and novel new actinide complexes, sometimes with isotopic labels, and, in addition to characterising them with the usual range of analytical techniques, will probe the covalency of the key actinide-ligand linkages with detailed NMR and computational studies to quantify the covalency. Our overall aim is, through the study of various related complexes and NMR nuclei, to build our understanding of actinide covalency.