Low oxidation state actinide heterolide complexes

该项目旨在发展低氧化态（OS）锕系元素（An 2+和An 3+）离子的化学，以更深入地了解影响其价电子构型（VEC），键合和反应性的性质，以及不同VEC驱动的发散化学的潜力。当代低OS的锕系元素化学定义了两类An 2+和An 3+离子，其中VEC可以使用以下两种形式描述：fn+1或fnd 1（注意，这些只是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相同金属，两者都存在。在这里，我们将利用一个模块化的分子设计，以目标低OS的锕系元素的离子，使用软供体配体，允许一个单一的变量（杂原子的身份）可以改变与配位环境的变化最小。这将提供前所未有的洞察这些离子的物理化学性质，以及控制其稳定性的因素。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-嵌段络合物，其中配体供体原子可以在对整体立体化学性质的最小变化的情况下改变; 2）使用适合于高级光谱表征的供体元素;3）通过磁性（SQUID）、磁共振（NMR、EPR）、X射线吸收光谱（在金属边缘）表征分子，以加深对其电子结构的理解。这种系统的方法还没有应用到这个新兴的研究领域，是一个合乎逻辑的下一步，以扩大其前沿。这项工作将产生的基础知识，通知未来的工作到配置控制的f-块离子，氧化还原驱动的镧系元素/锕系元素chemical.Questions：我们可以使用新的软施主配体分离低氧化态和锕系元素配合物？这些配合物的电子结构是什么，电子密度是在金属上还是在配体上？这会随着捐赠者的类型而改变吗？这些低氧化态配合物的反应与传统的锕系元素配合物相似，还是更像过渡金属？方法：设计和合成配体。使络合物处于容易获得的氧化态。将络合物还原为较低的形式氧化态。使用最先进的实验和理论方法进行表征。使用经典的过渡金属反应类研究反应性。Remit / themes：合成配位化学/计算和理论化学。凝聚态物质：电子结构。凝聚态物质：磁性和磁性材料。

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.