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

Subject Area Inorganic Molecular Chemistry - Synthesis and Characterisation
Solid State and Surface Chemistry, Material Synthesis
Term since 2017
Project identifier Deutsche Forschungsgemeinschaft (DFG) - Project number 338584285
 
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.
DFG Programme Research Grants
 
 

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