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

通过衍生化、阳离子交换、机理和反应性研究提高含有二元和三元 Zintl 阴离子的化合物的溶解度和多功能性

• 批准号: 338584285
• 负责人: Professorin Dr. Stefanie Dehnen
• 金额: --
• 依托单位: Institut für Nanotechnologie (INT)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/338584285?language=en
• 关键词: Improving; solubility; versatility; compounds; containing

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.

金属簇的研究为了解金属纳米颗粒或块体金属的形成的初始步骤提供了一个窗口，因为第一键的形成和种子簇的结构对于颗粒的后续生长起着至关重要的作用。似乎能够实现键活化——以其原始形状或作为活性材料的前体，但是，仍然存在许多悬而未决的问题，涉及所需组成和结构的簇的受控合成，以及它们在常见有机溶剂中的进一步活化和使用。这需要足够的溶解度。基于我们在 Zintl 化合物领域的成功工作，该研究计划解决了先前研究中出现的此类问题，并为 Zintl 簇化学领域提供了新的方向。该项目的起点是前体盐的合成。从这一点出发，我们的目标可以分为四个部分： WP1：从二元阴离子或三元 Zintl 相的盐中合成新的金属间化合物和异金属 Zintl 簇。迄今为止尚未探索的其他金属离子类型 WP2：Zintl 阴离子与空间要求高的 SiR3 基团的硅烷化，以及根据理论预测选择合适的候选者的后续反应 WP3：与 {M' 形成二元 Zintl 阴离子的衍生物。 (hmds)x} (x = 1, 2) 或 {M′(CO)x} 取代基，并研究它们在后续簇形成反应中的行为： Zintl 簇的反应性研究涉及有机偶联反应、小分子活化和通过使用紫外光进行的受控降解。所有合成和实验工作都将辅以必要的深入量子化学计算，以进一步了解结构和电子。这些系统的性质，并提供对其化学行为的重要见解。