Low oxidation state actinide heterolide complexes

低氧化态锕系杂化物配合物

• 批准号: 2904721
• 金额: --
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2904721
• 关键词: Low; oxidation; state; actinide; heterolide

This project seeks to develop the chemistry of low oxidation state (OS) actinide (An2+ and An3+) ions towards a deeper understanding of the properties that affect their valence electron configuration (VEC), bonding, and reactivity, and the potential for divergent chemistry driven by different VECs. Contemporary low OS, actinide chemistry has defined two classes of An2+ and An3+ ion where the VEC can be described using the following two formalisms: fn+1 or fnd1 (note that these simply describe an approximation of the configuration of the outermost electrons in these ions). In some cases both exist for the same metal with different coordination environments. Here we will exploit a modular molecular design to target low OS actinide An ions using soft donor ligands which allow a single variable (the identity of a heteroatom) can be changed with minimal changes to the coordination environment. This will afford unprecedented insight into the physicochemical properties of these ions, and the factors which govern their stabilities. We will achieve this by:1) synthesising low OS f-block complexes using modular frameworks where ligand donor atoms can be altered with minimal changes to the overall stereochemical properties; 2) using donor elements which are amenable to advanced spectroscopic characterisation;3) characterising molecules by magnetism (SQUID), magnetic resonance (NMR, EPR), X-ray absorption spectroscopy (at metal edges), to deepen understanding of their electronic structure. This systematic approach has not yet been applied to this nascent research area and is a logical next step to expand its frontier. This work will produce fundamental knowledge to inform future work into configuration control of f-block ions, and redox-driven lanthanide/actinide chemistry.Questions:Can we use novel soft-donor ligands to isolate low-oxidation state and actinide complexes?What is the electronic structure of these complexes, does the electron density reside on the metal or ligand?Does this change with the donor type?Do these low oxidation state complexes react like traditional actinide complexes, or more like transition metals?Approach:Design and synthesize ligands.Make complexes in readily available oxidation states.Reduce complexes to lower formal oxidation states.Characterize using state of the art experimental and theoretical approaches.Study reactivity using classical transition metal reaction classes.Remit / themes:Synthetic coordination chemistry/Computational and theoretical chemistry.Condensed matter: electronic structure.Condensed matter: magnetism and magnetic materials.

该项目致力于发展低氧化态(OS)鳗系元素(An2+和An3+)离子的化学，以更深入地了解影响其价电子配置(VEC)、成键和反应性的性质，以及不同VEC驱动的发散化学的可能性。当代低OS型元素化学定义了两类An2+和An3+离子，其中VEC可用以下两种形式描述：Fn+1或Fnd1(请注意，这两种形式仅描述了这些离子中最外层电子的近似构型)。在某些情况下，对于具有不同配位环境的同一金属，两者都存在。在这里，我们将利用模块化的分子设计，使用软给电子体配体来靶向低OS吖系元素AN离子，这使得可以在最小程度上改变配位环境的情况下改变单个变量(杂原子的身份)。这将提供前所未有的洞察这些离子的物理化学性质，以及控制它们稳定性的因素。我们将通过以下方式实现这一目标：1)使用模块化框架合成低OS f-嵌段配合物，其中配体给体原子可以在最小程度上改变整体立体化学性质；2)使用能够进行高级光谱表征的给体元素；3)通过磁性(SQUID)、磁共振(NMR，EPR)、X射线吸收光谱(在金属边缘)来表征分子，以加深对其电子结构的理解。这种系统的方法尚未应用于这一新的研究领域，是扩大其前沿的合乎逻辑的下一步。这项工作将产生基础知识，为未来的工作提供信息，以控制f-块离子的构型，以及氧化还原驱动的镧系元素/鳗系元素化学。问题：我们是否可以使用新型的软施主配体来分离低氧化态和鳗系元素络合物？这些络合物的电子结构是什么，电子密度是驻留在金属或配体上的吗？这是否会随着施主类型的变化而改变？这些低氧化态络合物是否会像传统的吖系元素络合物一样反应，或者更像过渡金属？方法：设计和合成配体。使络合物处于容易获得的氧化态。将络合物还原到更低的形式氧化态。使用最先进的实验和理论方法来表征。使用经典的过渡金属反应类来研究反应性。发表/主题：合成配位化学/计算和理论化学。凝聚态：电子结构。凝聚态：磁性和磁性材料。