Theses and Dissertations

Issuing Body

Mississippi State University

Advisor

Montiel-Pamla, Virginia

Committee Member

Webster, Charles

Committee Member

Emerson, Joseph

Committee Member

Creutz, Sidney

Committee Member

Mlsna, Todd

Date of Degree

8-7-2025

Original embargo terms

Visible MSU Only 2 Years

Document Type

Dissertation - Campus Access Only

Major

Chemistry

Degree Name

Doctor of Philosophy (Ph.D.)

College

College of Arts and Sciences

Department

Department of Chemistry

Abstract

In recent years, heterobimetallic complexes that incorporate a transition metal (TM) with a Group 13 element (Al, Ga, In) have demonstrated potential for activating challenging substrates. This area is growing and offers higher performance than the traditional single-metal catalytic approach. These complexes provide new strategies that can potentially enable cooperative bond activation through metal-metal cooperation. One important target for such bond activation is the aromatic C-N scission, a key transformation in the hydrodenitrogenation (HDN) process of the nitrogen compounds present in fossil fuels. These N-containing compounds are highly resistant to cleavage under mild conditions, thereby necessitating high temperatures and hydrogen pressure. Achieving selective CN bond cleavage in these substrates is essential for reducing NOₓ emissions from fossil fuel combustion, yet it remains difficult with conventional. Homogeneous systems. In this work, we explore the coordination behavior and electronic structure of Ru and Rh complexes supported by arene ligands and bearing Ga or Al Lewis acidic organo-fragments. Through the formation of zwitterionic, cationic, and Z-type complexes, these studies highlight the reactivity, versatility, catalytic application, and coordination behavior of organogallium, showing its potential for designing catalytic bimetallic systems. In Chapter I, we summarize the background and motivation for this work, focusing on the challenges of HDN, the role of N-heterocycles in fossil fuels, and the potential of bimetallic systems for cooperative bond activation. In Chapter II, the reactivity of Ru complexes with organogallium reagents, leading to the formation of Z-type and ion-pair species, with structural and DFT analysis revealing the nature of Ru–Ga interactions. In Chapter III, a series of zwitterionic and cationic Ru-carbazolyl complexes incorporating Al or Ga, along with their catalytic activity for regioselective hydroboration of N-heterocycles. In Chapter IV, Rh–carbazolyl zwitterionic complexes with Group 13 elements are synthesized and examined for their reactivity toward hydrogenation

Sponsorship (Optional)

Chemistry Division of the National Science Foundation (CAREER CHE-2145588)

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