Synthesis and Characterization of Pyridyl-1-azaallyl-based Pro-Ligands for Main-Group Metals

Paul, Riya (2025) Synthesis and Characterization of Pyridyl-1-azaallyl-based Pro-Ligands for Main-Group Metals. Masters thesis, Indian Institute of Science Education and Research Kolkata.

Text (MS Dissertation of Riya Paul (20MS065)) 20MS065_Thesis_file.pdf - Submitted Version Restricted to Repository staff only Download (1MB)

Abstract

This work deals with the synthesis and characterization of pyridyl-1-azaallyl-based pro-ligands designed to support main-group metals. Ligand design plays a crucial role in stabilizing electropositive main-group elements, which are often redox-inactive and prone to Schlenk equilibria. The goal was to develop chemically non-innocent, electron-rich, and kinetically robust ligand frameworks capable of promoting metal-ligand cooperation (MLC), an emerging concept in main-group chemistry. Pyridine-functionalized β-diketiminate analogues were synthesized in both bidentate and tridentate formats, and their electronic and structural features were elucidated using NMR spectroscopy and high-resolution mass spectrometry. These pyridyl-1-azaallyl scaffolds displayed features consistent with ligand non-innocence and tautomeric flexibility, critical for engaging in dynamic bonding with main-group metals. The potential of these pro-ligands in stabilizing Mg, Zn, and Al complexes has been explored, laying the groundwork for future investigations into reactivity and catalysis. An effort has also been made to understand how ligand architecture influences tautomeric distribution (keto-enol ratios) and the electronic environment of the metal center, which are vital in developing cooperative, functional ligand systems for small-molecule activation and catalysis.

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