Executive Summary : | Over the past decade, the focus on non-heme chemistry has been on the generation and stability of intermediates and their reactivity studies. Tools such as external oxidants, dioxygen activation, electron transfer, and singlet oxygen have been used to generate intermediates. However, there is limited literature on tuning the coordination sphere by inducing electronic and structural perturbations around the metal center. One strategy is to employ halides and pseudo halides in axial or equatorial positions. The present proposal aims to use asymmetric ligand architecture like N4X, where X occupies either at the axial or equatorial positions. This concept will lead to a better understanding of the influence of electronic and structural perturbations around the metal center in controlling reaction rates and fine-tuning the reaction mechanism. The influence of controlling redox potentials of the metal center in such intermediates will lead to a better understanding of enzymatic reactions. The proposed proposal involves designing and synthesizing a ligand framework to explore the formation, stability, and reaction mechanism of metal oxygen adducts. It is important to note that not all ligand frameworks support the generation of such metal oxygen adducts. To address this limitation, the proposal proposes using the known N5 type of ligands and systematically introducing hetero atoms to explore the results. More complex ligand systems would be synthesized based on the outcome. The successful outcome of the proposed work will shed light on understanding enzymatic reactions and how nature employs these to achieve regio and stereo reactions. A detailed experimental and computational tool would be employed for a comprehensive study on the influence of hetero atoms in inducing structural and electronic perturbations, tuning overall reaction rates, and controlling reaction pathways. |