Research Projects

The development of diverse ligand frameworks has driven the success of homogeneous catalysis, enabling precise control of catalytic systems. Cyclic diamino-carbenes (NHCs) are notable for their strong σ-donor properties and tunable structures for various uses. While stable carbenes like NHCs are well-studied, transient carbenes such as CAACs/CAArCs are less characterized due to their instability. Despite their proposed importance in catalysis, their roles remain uncertain due to reliance on indirect observation methods. This challenge limits direct understanding of their mechanisms, leaving debate about their electronic properties, coordination, and catalytic behavior. Scientific Objectives: This project uses computational methods to explore the reactivity and stability of transient carbenes. We aim to design optimized NHC and CAAC/CAArC ligands with specific properties to boost catalytic efficiency with metal catalysts. The work combines theoretical predictions with experimental validation to enhance the effectiveness of transient carbenes in catalysis, advancing their practical use. Hypothesis: The project hypothesizes that optimizing CAACs and NHC ligands computationally can enhance the stability and catalytic performance of the transient carbenes. Modifying these ligands with bulky, electron-rich substituents aims to improve reactivity and selectivity, particularly in redox metal catalysis with metals like gold, copper, and others. Advanced computational techniques will visualize steric and electronic properties to show how modifications affect carbene stability and reactivity. Approach: 1. Computational Ligand Design: Using Density Functional Theory (DFT), along with tools like SambVca and NEST analysis, we will develop models that predict the steric and electronic effects of modified carbene ligands. These tools will allow us to map ligand properties that promote carbene stabilization and selectivity. 2. Mechanistic Simulation: Computational models will study reaction pathways to understand the intermediate and transition states, shedding light on the role of carbenes catalytic cycles. 3. Synthesis and Testing: Leveraging computational results, selected carbene ligands will be synthesized and tested in collaboration with synthetic chemists and evaluated for their performance in catalytic applications. Significance: Achieving the research objectives will have profound implications for the understanding and application of carbenes in catalysis. Computationally driven carbene ligand design offers a powerful approach to enhancing catalyst stability and fine-tuning chemo-, regio-, and enantioselectivities in reactions. This work may lead to more robust, selective, and efficient catalytic systems by properly understanding the role of designed carbenes in catalytic mechanisms. This would advance both the basic chemistry of carbenes and real-world applications in synthetic catalysis.