Improving solubility and versatility of compounds containing binary and ternary Zintl anions through derivatization, cation exchange, mechanistic, and reactivity studies

金属簇的研究提供了一个窗口，在金属纳米粒子或大块金属的形成的初始步骤，作为第一键的形成和种子簇的结构起着至关重要的作用，为随后的颗粒的生长。此外，这种簇似乎能够激活键-以其原始形状或作为活性材料的前体。然而，许多悬而未决的问题仍然存在，关于所需组成和结构的簇的受控合成，以及它们在普通有机溶剂中的进一步活化和使用，这需要足够的溶解度。继我们在Zintl化合物领域的成功工作之后，这项研究计划解决了以前研究中出现的问题，并在Zintl簇化学领域提供了新的方向。该项目的起点将是合成二元或三元阴离子的前体盐。从这一点上，我们的目标可以分为四个部分：WP 1：合成新的intermetalloid和heterometallic Zintl簇从盐的二元阴离子或三元Zintl相结合，到目前为止未开发的类型的额外的金属离子。WP 2：Zintl阴离子与空间要求高的SiR 3基团的甲硅烷基化，以及随后的反应，在理论预测的基础上选择合适的候选物。WP 3：二元Zintl阴离子与{M′（hmds）x}（x = 1，2）或{M′（CO）x}取代基的衍生物的形成及其在随后的簇形成反应中的行为研究WP 4：Zintl团簇的反应性研究，包括有机偶联反应、小分子活化和通过使用UV光的受控降解。所有的合成和实验工作都将得到必要的深入量子化学计算的补充，以进一步了解这些系统的结构和电子性质，并对其化学行为提供关键的见解。

The investigation of metal clusters provides a window into the initial steps in the formation of metal nanoparticles or bulk metal, as the formation of first bonds and the structures of seed clusters play a crucial role for the subsequent growth of a particle. Furthermore, such clusters seem to enable bond activation – in their original shape or as precursors of active materials. However, many open questions remain, concerning the controlled synthesis of clusters of a desired composition and structure, as well as their further activation and usage in common organic solvents, which requires sufficient solubility. Following on from our successful work in the field of Zintl compounds, this research program addresses such issues that have arisen in previous studies, and offers new directions in the field of Zintl cluster chemistry. The starting point of the project would be the synthesis of precursor salts of binary or ternary anions. Our objectives from this point can be divided into four sections: WP1: Synthesis of new intermetalloid and heterometallic Zintl clusters from salts of binary anions or ternary Zintl phases in combination with so far unexplored types of additional metal ions. WP2: Silylation of Zintl anions with sterically demanding SiR3 groups, and subsequent reactions, upon selection of suitable candidates on the basis of theoretical predictions. WP3: Formation of derivatives of binary Zintl anions with {M′(hmds)x} (x = 1, 2) or {M′(CO)x} substituents, and investigation of their behavior in subsequent cluster formation reactions. WP4: Reactivity studies of Zintl clusters with regards to organic coupling reactions, small molecule activation and controlled degradation through the use of UV light. All synthetic and experimental work will be complemented with essential in-depth quantum chemical calculations to gain further understanding of the structural and electronic nature of these systems, as well as provide crucial insight to their chemical behavior.