Thermodynamic and Kinetic Comparison of sigma-Hole Catalysts

该项目将推动Sigma-Hole相互作用及其在有机催化中的应用。具体地说，我们将分析这些相互作用在气相(通过离子迁移率质谱仪)以及在溶液中(通过核磁共振滴定)的强度。然后，我们将把这些热力学信息与从不同模型反应中获得的动力学数据关联起来。在所有情况下，实验调查将伴随着高水平的计算调查，以提供关于这些相互作用的性质和任何观察到的反应性趋势的更多信息。因此，我们的研究一方面将为溶剂效应和这些非共价相互作用的其他关键方面提供深入的见解。另一方面，将动力学分析与热力学参数相结合，将加深我们对Sigma-Hole催化的理解。

This project will advance the field of sigma-hole interactions and their application in organocatalysis. Specifically, we will analyze the strengths of these interactions both in the gas phase (via ion mobility mass spectrometry) as well as in solution (via NMR titrations). We will then correlate this thermodynamic information with kinetic data obtained from different model reactions. In all cases, the experimental investigations will be accompanied by high-level computational investigations to provide additional information on the nature of these interactions and any observed reactivity trends. Therefore, our investigations will –on the one hand– provide deep insights into solvent effects and other crucial aspects of these noncovalent interactions. On the other hand, the kinetic analysis incombination with the thermodynamic parameters will enhance our understanding of sigma-hole catalysis.