Designing Earth Abundant Metal Catalysts of Phenalenyl Ligands based on Metal-Ligand Cooperativity

Chakraborty, Soumi (2022) Designing Earth Abundant Metal Catalysts of Phenalenyl Ligands based on Metal-Ligand Cooperativity. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Soumi Chakraborty (14IP033)) 14IP033.pdf - Submitted Version Restricted to Repository staff only Download (12MB)

Abstract

In the field of homogeneous catalysis, designing catalysts with earth-abundant first-row transition metals is considered to be attractive as they provide a green, sustainable, cost-effective and environmentally benign synthetic protocol. In this regard, the combination of redox-active ligand moieties with 3d transition metal has been considered a powerful strategy to promote multi-electron catalytic transformations through metal-ligand cooperativity, frequently observed in various biological metalloenzymes such as galactose oxidase and cytochrome P450. In present thesis, design of various bio-inspired first-row transition metal catalysts have been developed for catalysis and small molecule activation. The present thesis is discussed in three chapters. Chapter 1 provides a brief introduction on previous development of redox-active ligand-based base metal complexes and their reactivity. Chapter 2 presents adetailed discussion of the results obtained in the present investigation including catalytic outcomes, experimental studies, and mechanistic investigations. This chapter is subdivided into four sections: the first section presents a long-lived Fe(III) complex bearing bidentate phenalenyl (O,O-PLY) ligand for catalytic C-H arylation of (hetero)arenes at room temperature; the second section deals with tridentate phenalenyl (N,N,O-PLY) ligand coordinated Mn(I) complex for catalytic hydrosilylation of ester using inert and inexpensive PMHS under ambient conditions. The next two sections describe catalytic carbon dioxide (CO2) activation: the third section includes N,N,O-PLY ligated Cr(III)-complex for N-formylation of primary amide using CO2 (1 atm) as reagent; the fourth section describes Mn(I)-N,N,O-PLY catalyst for N-formylation of lactams and secondary amides using CO2 (1 atm) as C1 source at room temperature. The highlights of the present investigation and possible future directions are summarized at the end of this chapter. Finally, Chapter 3 describes all detailed experimental procedures, characterization dataand DFT calculations.

Actions (login required)

View Item