Development, Characterization, and Corresponding Reactivity of First-Row Transition Metal Complexes with Redox-Active Catecholamine Ligands Restricted; Files Only

Abstract

Over the decades, various research has reported the potency of organometallic complexes as efficient catalysts to put previously unachievable reactions into practice. Second and third-row transition metals are predominantly used from the outset as they exhibit a high catalytic activity in multi-electron transformations, yet the scarcity and extractability of those metals make the mass industrial production and the subsequent waste treatment fraught with limitations. With the goal to design environmentally friendly, low-cost, efficient catalysts, chemists begin to use first-row transition metals, which are far more abundant in nature, to synthesize catalysts. The major challenge for this is that first-row transition metals exhibit a relatively low reactivity to promote multi-electron catalytic reactions under natural conditions. This research aims to approach the conundrum by developing ligands that can modify and enhance the reactivity of the first-row transition metals through coordination. Specifically, the research focus is on the development of first-row transition metal complexes that incorporate the redox-active catecholamine ligands along with a close examination regarding the corresponding catalytic activity. Two types of ligands, N,N'-(azanediylbis(2,1-phenylene))bis(2,3-dihydroxybenzamide) (H7L^CAT) and 2,3-dihydroxy-N-(2-(phenylamino)phenyl)benzamide (H4L^CAT) have been designed, synthesized, and characterized through NMR spectroscopy. Both ligands contain nitrogenous and catechol systems with the objective to enable a versatile coordination and further enhance the reactive performance of the metal-ligand complexes. Metalation has been performed to synthesize bimetallic complexes with Iron (II), Cobalt (II), Zinc (II), Copper (II), and Nickel (II). The metal-ligand complexes were firstly characterized through single crystal X-ray diffraction to obtain the 3D structures, and further analyzed with NMR spectroscopy, cyclic voltammetry, and mass spectroscopy. Preliminary oxidative reactivity studies were then conducted and closely monitored with UV-Vis Spectroscopy.

Table of Contents

Chapter 1: Historical and Evolutionary Trajectory of Redox-Active Ligands in First-Row Transition Metal Catalysis…………………………………………...………………………..1

Chapter 2: Synthesis, Characterization, and Preliminary Reactivity Study of Iron (II), Cobalt (II), Zinc (II), Copper (II), and Nickel (II) Complexes with Catecholamine Redox-Active Ligands……………………………………………………………………………...………....8

Chapter 3: Conclusion and Future Direction…......…………………………………………26

Experimental Section…...….……………………………………………………………….28

Reference…………………………………………………………………………………….34

About this Honors Thesis

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School	Emory College
Department	Chemistry
Degree	B.S.
Submission	Honors Thesis
Language	English
Research Field	Chemistry, Inorganic
Parola chiave	Inorganic Transition Metal Catalysis
Committee Chair / Thesis Advisor	Cora MacBeth, Emory University
Committee Members	Craig Hill, Emory University Simon Blakey, Emory University Richard Himes, Emory University

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