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Prescribed-Time Nash Equilibrium Seeking For Pursuit-Evasion Game Under Intermittent Control With Undirected/Directed Graph, Lei Xue, Jianfeng Ye, Yongbao Wu, Jian Liu, D. C. Wunsch Jan 2025

Prescribed-Time Nash Equilibrium Seeking For Pursuit-Evasion Game Under Intermittent Control With Undirected/Directed Graph, Lei Xue, Jianfeng Ye, Yongbao Wu, Jian Liu, D. C. Wunsch

Electrical and Computer Engineering Faculty Research & Creative Works

This paper studies the prescribed-time Nash equilibrium (PTNE) seeking problem of the pursuit-evasion game (PEG) with second-order dynamics under the intermittent control (IC) strategy. To achieve Nash equilibrium (NE) in a user-defined prescribed-time, a time-varying high-gain function is incorporated into the design. The core challenge lies in applying IC to NE seeking, which complicates the convergence analysis and control design. To address this sticking point, we construct an auxiliary function and propose a Lyapunov function considering second-order dynamics to solve the PTNE seeking problem of PEG. Building upon the results for undirected graphs, we further extend our findings to directed …


Active And Reactive Power Flow Control Of The Dual Active Bridge Converter, Lauryn Morris, Thomas W. Francois, Jonathan Saelens, Oroghene Oboreh-Snapps, Arnold Fernandes, Praneeth Uddarraju, Sophia A. Strathman, Jonathan W. Kimball Jan 2025

Active And Reactive Power Flow Control Of The Dual Active Bridge Converter, Lauryn Morris, Thomas W. Francois, Jonathan Saelens, Oroghene Oboreh-Snapps, Arnold Fernandes, Praneeth Uddarraju, Sophia A. Strathman, Jonathan W. Kimball

Electrical and Computer Engineering Faculty Research & Creative Works

The Dual Active Bridge (DAB) is a reliable and efficient converter capable of providing bi-directional power transfer and galvanic isolation. An ac-ac DAB can control both active and reactive power flow. The present work introduces a combined feedback/feed-forward current control system, utilizing the calculated and measured converter currents translated into the dq reference frame, to control the output power. The system was simulated in PLECS to demonstrate the control algorithm's ability to track the dq currents and provide the necessary output power.


Improving The Operator-Swarm Dynamic Under Mental Fatigue Constraints In Search And Rescue Operations, Jordan Morrow Jan 2025

Improving The Operator-Swarm Dynamic Under Mental Fatigue Constraints In Search And Rescue Operations, Jordan Morrow

Masters Theses

"Human-robot applications that allow for work to be done remotely are largely dependent on the lassitude of the operators. The exhaustion of these operators is a result of work completion and duration. Previous research attempts to evaluate the impact on reaction by quantiying human weariness. This paper examines how human weariness affects the human-robot dynamic in UAV-assisted search and rescue missions. An explanation of the connection between mental exhaustion and operator responsiveness over prolonged durations is provided by the search and rescue operations using UAV swarms (SAROUS) model. Through the use of artificial intelligence, SAROUS is modernized. This allows the …


Applying Human System Integration Principles To The Investigation, Design And Validation Of Interventions For Self-Escape In Underground Mines, Eugene Adubofour Gyawu Jan 2025

Applying Human System Integration Principles To The Investigation, Design And Validation Of Interventions For Self-Escape In Underground Mines, Eugene Adubofour Gyawu

Doctoral Dissertations

This dissertation investigates the use of human systems integration (HSI) to develop technologies for miners’ self-escape during a mine emergency, addressing barriers that compromise miner safety during emergencies.

Recognizing the inherently hazardous nature of underground mining, this study has three core objectives: (1) assessing miners' perceptions of proposed self-escape interventions, (2) designing interventions based on these insights, and (3) validating their effectiveness using experimental testing. This work evaluates self-escape interventions for both coal and metal/non-metal miners using scenario-based surveys, information design reviews, label designs and experimental testing methods varying across three distinct studies.

Results reveal that miners identified improvements to …


Implication And Applications Of Machine Learning On Biomedical Images, Jason Hagerty Jan 2025

Implication And Applications Of Machine Learning On Biomedical Images, Jason Hagerty

Doctoral Dissertations

Medical imaging ranges in modality including computer tomography imaging, x-ray imaging, digital microscopy, and macro-focus dermoscopy images. The latter two modalities are the focus of the presented work.

To perform a diagnostic evaluation on the captured dermoscopy image, it begins with what is usually a labor-intensive operation that requires an expert to perform the initial segmentation for localizing a region of interest (ROI). Once that ROI is obtained, a physician with years of training and experience will observe biological markers that can be used to visually differentiate whether a lesion is benign or malignant. A similar process is used for …


Novel Nano-Formulations Based On Flash Nanoprecipitation For Ocular Drug Delivery, Lin Qi Jan 2025

Novel Nano-Formulations Based On Flash Nanoprecipitation For Ocular Drug Delivery, Lin Qi

Doctoral Dissertations

Effective ocular drug delivery has always been a challenge for clinical and research. Although many nanotechnology-based formulations have been developed and showed great potential in ocular drug delivery, this is far from enough to meet clinical requirements. These studies aimed at the design and synthesis of novel nanoparticles using multi-inlet vortex mixer (MIVM) to improve ocular drug delivery efficiency. The first project involves packaging two different anti-glaucoma drugs, brimonidine (BM) and betaxolol (BX), into solid drug nanoparticles (SDNs) by MIVM, which can achieve both functions, reducing aqueous humor production and promoting aqueous humor efflux. The studies demonstrate that the SDNs …


Characterization And Deportment Of Anode Impurities In Copper Electrorefining, Charles Michael Campbell Jan 2025

Characterization And Deportment Of Anode Impurities In Copper Electrorefining, Charles Michael Campbell

Doctoral Dissertations

The objective of this research was to study the deportment of the group 15 elements, arsenic, antimony and bismuth during copper electrorefining. Samples were collected from six industrial copper anodes with different compositions. Specimens were physically characterized and electro refined to understand the differences in the behavior of selected impurities. Inclusions in the cast metal structures were characterized using automated scanning electron microscopy and energy dispersive spectroscopy to measure and correlate their size, shape and composition. Arsenic and lead were found to have a positive correlation between concentration and size of inclusions. Using wavelength dispersive spectroscopy, multiphase inclusions were examined, …


Data-Driven Mulitiscale Modeling Of Electrochemical Transport, Non-Linear Electrical Contact, And Additive Manufacturing Processes, Emmanuel Olugbade Jan 2025

Data-Driven Mulitiscale Modeling Of Electrochemical Transport, Non-Linear Electrical Contact, And Additive Manufacturing Processes, Emmanuel Olugbade

Doctoral Dissertations

The growing demand for high-efficiency energy systems and advanced manufacturing technologies requires predictive frameworks that link atomic-scale physics with engineering-scale performance. This dissertation develops a unified multiscale modeling approach that integrates molecular dynamics, density functional theory, finite-element analysis, and machine learning to connect structure, transport, and performance across materials and processes. Depending on the interactions involved, the framework employs loose coupling for parameter transfer, tight coupling for two-way feedback, and hybrid coupling where machine-learning surrogates accelerate high-fidelity simulations while retaining physical interpretability. In electrochemical systems, an XGBoost-enhanced single-particle model reproduces P2D-level electrolyte potential dynamics at roughly one-hundredth the computational cost, …


Characterization And Modeling Of Properties Of Unsaturated And Partially Damaged Cement-Based Materials, Rezwana Binte Hafiz Jan 2025

Characterization And Modeling Of Properties Of Unsaturated And Partially Damaged Cement-Based Materials, Rezwana Binte Hafiz

Doctoral Dissertations

"Transport properties, governing the resistance of cement-based materials to harmful substances are essential considerations for long-term performance. This study addressed the often-overlooked dimension of transport properties in unsaturated cement-based materials, crucial as most concrete structures face variable environmental conditions, leading to partial saturation. A two-scale model was introduced, enhancing our comprehension of transport properties in conditions reflecting real-world scenarios. Empirical correlation representing bulk paste characteristics was established, facilitating the upscaling of properties to mortar and concrete. The model was extended to predict the transport properties of mortar as well.

Environmental factors can contribute to the degradation of cement-based materials, with …


Additive Manufacturing Of Multifunctional Materials And Composites, John Michael Pappas Jan 2025

Additive Manufacturing Of Multifunctional Materials And Composites, John Michael Pappas

Doctoral Dissertations

"This research focused on developing fundamental knowledge of process-material interactions for additive manufacturing of multifunctional materials that are highly desirable in high-tech industries for potential weight and space savings. Multifunctional materials are very sensitive to defects, which severely hinder performance. Thus, defect formation was systematically studied to develop strategies and methodologies to efficiently fabricate high-performance materials and composites. Blown-powder-based laser additive manufacturing of transparent spinel ceramics was investigated to reduce porosity and cracking, defects that hindered transparency and mechanical properties. A systematic study of processing parameters revealed that laser power and powder flow rate had the largest effects on defect …


Exploring The Feasibility Of Innovative Integration Of Phase Change Materials For Thermo-Adaptive Asphalt Pavements, Farshad Saberi Kerahroudi Jan 2025

Exploring The Feasibility Of Innovative Integration Of Phase Change Materials For Thermo-Adaptive Asphalt Pavements, Farshad Saberi Kerahroudi

Doctoral Dissertations

"Current research examined the feasibility and efficiency of employing phase change materials (PCMs) in asphalt pavement materials to result in thermo-adaptive asphalt pavement. The PCM was introduced to the asphalt materials in three different scales, including asphalt binder, asphalt mastic, and asphalt mixture. After investigating asphalt at different scales, mix blending method was found as the easiest method without any complexity to mix asphalt binder with PCM. The testing results could reveal an improvement in the high temperature performance of asphalt binder without sacrificing the low temperature performance with the presence of PCM and Gilsonite. Also, introducing PCM to asphalt …


Investigation Of The Transport And Plugging Behavior Of Preformed Particle Gels (Ppgs) In Fractures For Conformance Control In Carbonate Reservoirs, Abdulaziz A. Almakimi Jan 2025

Investigation Of The Transport And Plugging Behavior Of Preformed Particle Gels (Ppgs) In Fractures For Conformance Control In Carbonate Reservoirs, Abdulaziz A. Almakimi

Doctoral Dissertations

This study aims to systematically evaluate the performance of preformed particle gels (PPGs) in fractured carbonates mainly through a series of core flooding experiments. Carbonate reservoirs exhibit unique features of heterogeneity and pore geometry, while (PPGs) are known for their plugging efficiency, deformability, and dehydratable nature. The main goal of gel injection in fractured reservoirs is to place a gel pack appropriately into the fracture, diverting injected fluid to the oil-bearing matrix and reducing excessive water production. However, considerable dehydration of (PPGs) is possible at the adjacent matrix and within the fracture, which could lead to a filter-cake formation and/or …


Effect Of Thermomechanical Processing And Heat Treatment On The Microstructure And Mechanical Properties Of Ultra-High Strength Steels, Rogerio Antao Cardoso Jan 2025

Effect Of Thermomechanical Processing And Heat Treatment On The Microstructure And Mechanical Properties Of Ultra-High Strength Steels, Rogerio Antao Cardoso

Doctoral Dissertations

"A martensite-based and an austenite-based Fe-Mn-Al steels were investigated aiming the pilot-scale production of steels that meet military specifications for Rolled Homogeneous Armor (RHA) and High-hardness Armor (HHA) plates. Each material underwent specific thermomechanical processes and the following hardness, Charpy V-notch (CVN) impact toughness at -40 °C and room-temperature tensile properties were correlated with the resulting microstructures.

Specimens of the martensitic steel were austenitized at 1010 °C, quenched and tempered at 150, 175, 200, 225 and 250 °C for times up to four hours. As for the Fe-Mn-Al steel, its hot rolling schedule was design to promote strain accumulation in …


Processing And Densification Of Multi-Phase High-Entropy Ceramics, Steven Smith Jan 2025

Processing And Densification Of Multi-Phase High-Entropy Ceramics, Steven Smith

Doctoral Dissertations

"This work focuses on the processing and densification of multiphase, high-entropy ceramics to promote their use in friction stir welding technologies. Several high-entropy systems including high-entropy borides, carbides, and their composites were produced. Boro/carbothermal and carbothermal synthesis were used to produce high-entropy powders from oxide powder mixtures. Composites of high-entropy borides and high-entropy carbides were produced using a sequential approach to produce both phases. The carbide was first produced using carbothermal reduction, then ZrH2 and B4C were added to the carbide powder to produce the high-entropy boride phase. The resulting powder was densified by spark plasma sintering and pressureless sintering, …


Application Of Artificial Intelligence Techniques To Improve Leadership Decision Making With Uncertainty, Michael David Parrish Jan 2025

Application Of Artificial Intelligence Techniques To Improve Leadership Decision Making With Uncertainty, Michael David Parrish

Doctoral Dissertations

"Every good leader is a good manager, but not every good manager is a good leader. The difference between the leader and the manager is critical decision-making. Today’s decision-making environment is characterized as Volatile, Uncertain, Complex, and Ambiguous (VUCA). With the exponential increase in the technical capabilities of systems, the human has become the weakest link in the use of such systems. To remain relevant, good leaders must continuously adapt to new advances in technology and processes.

The research contributions of this work provide several unique and novel solutions for leaders to utilize artificial intelligence tools to improve and optimize …


Selected Topics In Blockchain-Aided Iot Inference, Yiming Jiang Jan 2025

Selected Topics In Blockchain-Aided Iot Inference, Yiming Jiang

Doctoral Dissertations

"Blockchain has recently been considered in the Internet of Things (IoT) to secure data exchanges and storage across various engineering applications. This newly emerging blockchain-aided IoT (BIoT) network has been applied to a great deal of security-related applications. However, the BIoT still has the vulnerability that can be exploited by attackers, potentially impairing the performance of BIoT applications. Despite this, research addressing the vulnerability has been limited. This work presents four studies aimed at addressing critical gaps in current BIoT research.

The first study introduces a Time-Restricted Double-Spending Attack (TR-DSA) model for Proof-of-Work (PoW)-based blockchains, where the adversary only conducts …


A Hybrid Data Processing, Computational Intelligence, And Complex Systems Modeling Approach For Describing And Predicting The Bitcoin Market, Oluwadamilare Akinpelu Omole Jan 2025

A Hybrid Data Processing, Computational Intelligence, And Complex Systems Modeling Approach For Describing And Predicting The Bitcoin Market, Oluwadamilare Akinpelu Omole

Doctoral Dissertations

"The Bitcoin market, like traditional financial markets, is a complex system with intricate interdependencies and nonlinear interactions among various market elements. This, coupled with the inherent uncertainty and high volatility present, makes predicting Bitcoin price movements difficult. The lack of understanding of the underlying market dynamics often results in significant losses for investors and traders. Existing studies have focused on the use of predictive models, which have not sufficiently captured the complexities of the market and cannot forecast extreme market events. This research endeavors to bridge this gap by combining data processing techniques, computational intelligence, and complex systems theory to …


Atmospheric Transport Of Radionuclides, Meteorological Data Mining & Synthesis For Site Data Supplementation, Ben Yao Sonpon Jan 2025

Atmospheric Transport Of Radionuclides, Meteorological Data Mining & Synthesis For Site Data Supplementation, Ben Yao Sonpon

Doctoral Dissertations

"This research aligns with the NRC's vision of implementing risk-informed decision-making to support its regulatory charter. The suite of tools developed includes automated procedures for data mining and extracting meteorological (met) data from various national and regional repositories. A second data analytics tool automates the process of data fusion into a uniform format while preserving data fidelity. Autocorrelations were then established, and correlation coefficients were calculated between the Callaway Nuclear Power Plant (Callaway) and nearby off-site weather stations. The complexity of these correlations depends on factors such as physical proximity, geographic features, and topology, potentially necessitating multivariate analysis (MVA). Furthermore, …


Metal-Free Photoredox Catalysis For The S-Trifluoromethylation Of Thiols And Investigation Of Ph-Dependent Decontamination Of Dimethyl Chlorophosphate, A Nerve Agent Simulant, Via Hydrolysis With Azoles, Raheemat Rafiu Jan 2025

Metal-Free Photoredox Catalysis For The S-Trifluoromethylation Of Thiols And Investigation Of Ph-Dependent Decontamination Of Dimethyl Chlorophosphate, A Nerve Agent Simulant, Via Hydrolysis With Azoles, Raheemat Rafiu

Doctoral Dissertations

"Organofluorine chemistry plays a critical role in synthetic chemistry due to the unique properties of fluorine. However, the S-trifluoromethylation of thiols remains underexplored, with existing methods often relying on toxic and expensive organometallic catalysts. Given the advantages of S-trifluoromethylated compounds, including enhanced pharmacological activity and improved metabolic stability, we developed a green and cost-effective method for the synthesis of S-CF3 compounds using diacetyl as the organic catalyst and Langloi's reagent as the trifluoromethylating reagent. This reaction, which proceeds under mild conditions using visible light photoredox catalysis, works across various substrate scopes, including aromatic, heteroaromatic, and aliphatic thiols.

Chemical Warfare Agents …


Shock Wave And Vortex Ring Dynamics From Explosively Driven Shock Tunnels, Rachel Louise Bauer Jan 2025

Shock Wave And Vortex Ring Dynamics From Explosively Driven Shock Tunnels, Rachel Louise Bauer

Doctoral Dissertations

"Blast and shock tubes are frequently used to create shock waves to study their effects and impacts on structures, humans, and personal protective equipment. These tubes are also found in other industries including wind tunnels for aerodynamic testing, jet engines for propulsion research, spacecraft reentry simulations, and industrial applications such as material testing and high-velocity impact studies. Despite their widespread use, there is no standard design, with variations in geometry, size, and energy sources. Current research only evaluates the peak pressure of the shock wave produced and does not consider the effects of changing the size or geometry of the …


Lifelong Machine Learning With Adaptive Resonance Theory, Sasha Petrenko Jan 2025

Lifelong Machine Learning With Adaptive Resonance Theory, Sasha Petrenko

Doctoral Dissertations

"This publication option dissertation is composed of three papers concerning the study of the problem lifelong machine learning with Adaptive Resonance Theory (ART) algorithms. Lifelong learning (L2) is a challenging machine learning paradigm that both encompasses and formalizes the fields of continual learning and incremental learning. The field is concerned with the mitigation of the phenomenon of catastrophic forgetting whereby learning agents that are faced with incrementally novel information deleteriously overwrite previous knowledge if that learning process is not regularized to counteract this consequence. ART algorithms solve this stability-plasticity dilemma by optimally assigning learning to categories or instantiating new knowledge …


Investigation Of Shockwave Behavior To Inform Helmet Design Using Schlieren Imagery And Free-Field Blasts, Cody Jh Thomas Jan 2025

Investigation Of Shockwave Behavior To Inform Helmet Design Using Schlieren Imagery And Free-Field Blasts, Cody Jh Thomas

Doctoral Dissertations

"Ballistic resistance of military helmet designs is a prioritized feature to protect warfighters from traumatic brain injury. However, injuries from shock-based threats have not been optimized for warfighter protection and have resulted in the prevalence of blast-induced traumatic brain injury (bTBI). Research gaps were identified in understanding the under wash effect using free field blasts and schlieren imagery. Thus, the following were investigated: (1) overpressure changes on a warfighter’s head due to directionality from a blast, (2) shock wave dampening effects of viscoelastic materials in helmets, and (3) geometric effects of a helmet brim design in the reduction of bTBI. …


Nmr Relaxometry Approach For The Detection Of Asphalt Binder Performance Properties, Rebecca Herndon Jan 2025

Nmr Relaxometry Approach For The Detection Of Asphalt Binder Performance Properties, Rebecca Herndon

Doctoral Dissertations

"Asphalt is a necessary material for transportation infrastructure. Understanding the material properties of asphalt binders is critical for improving infrastructure and enhancing the lifetime of pavements. While the physical properties of asphalt binders are well-defined by standard procedures and parameters, the chemical environment lacks definition. Physical parameters like viscosity and stiffness are traditionally used to differentiate asphalt binders, describe aging, and indicate the impact of additives. However, these tests have limited insight into the material's chemical environment. Therefore, a nondestructive analytical technique, nuclear magnetic resonance (NMR) relaxometry, was employed to investigate the chemical environment of asphalt binders. Although NMR relaxometry …


Sensor Embedding And Thermal Monitoring Strategies For Laser-Foil-Printing Additive Manufacturing, Tunay Turk Jan 2025

Sensor Embedding And Thermal Monitoring Strategies For Laser-Foil-Printing Additive Manufacturing, Tunay Turk

Doctoral Dissertations

"This work investigates Laser Foil Printing (LFP), a novel metal additive manufacturing (AM) process that fabricates parts layer-by-layer using metal foils. To enhance LFP productivity, the process steps were optimized, and an 88.1% reduction in processing duration was achieved. A unique aspect of this study was the introduction of laser polishing as an edge polishing technique within the LFP process. This innovative approach, employing an overlapping spiral pattern, leverages selective laser remelting and erosion to effectively suppress elevated edges. To stabilize the molten melt pool, a discrete spot scanning strategy was implemented. The fabricated parts were subjected to detailed analysis, …


New Topologies For High Voltage Gain Dc-Dc Power Electronic Converters – Theoretical Analysis And Experimental Validation, Saeed Habibi Jan 2025

New Topologies For High Voltage Gain Dc-Dc Power Electronic Converters – Theoretical Analysis And Experimental Validation, Saeed Habibi

Doctoral Dissertations

"This dissertation is focused on developing and analyzing new high voltage gain DC-DC power electronic converters. The proposed converters in this dissertation are suitable candidates for connecting low voltage sources such as photovoltaic (PV) panels or fuel cell (FC) stacks to a DC microgrid or DC link of an inverter. The proposed converters provide desired characteristics such as high voltage gain at a low or medium duty cycle values, low voltage stress on power semiconductors, and continuous input current. Initially, the research introduces three novel converter topologies: First, two quadratic converters based on the combination of a three-winding coupled inductor …


Advancing Refuge Alternatives In Mine Emergencies Using Advanced Numerical Simulation, Kutay Emre Karadeniz Jan 2025

Advancing Refuge Alternatives In Mine Emergencies Using Advanced Numerical Simulation, Kutay Emre Karadeniz

Doctoral Dissertations

"Incidents and emergencies within underground coal mines can result in severe injuries or even loss of life, particularly due to the hazardous nature of mine explosions. One of the options for the miners to protect themselves from these hazards is to be sheltered in a refuge alternative (RA). However, the literature lacks an analysis of survivability constraints and the structural integrity of RAs when exposed to geomechanical changes and the ability to withstand the impact of coal mine explosions. In this study, based on the utilization and survivability constraints, basic human requirements and the required physical specifications of RAs during …


Vibration Modeling Of Rectangular Plates And Application To Solar Cell Dust Mitigation, Jeremiah John Rittenhouse Jan 2025

Vibration Modeling Of Rectangular Plates And Application To Solar Cell Dust Mitigation, Jeremiah John Rittenhouse

Doctoral Dissertations

"Many engineering structures can be modeled as rectangular plates, including solar cells. Carefully controlled plate vibration can be useful to solve an engineering problem, such as lunar dust accumulation on solar cells, which blocks light and reduces power generation. For this application, plate vibration at resonance is studied and used experimentally to eject lunar dust from a solar cell.

Piezoelectric actuator placement on the inactive side of a solar cell to induce vibration dust mitigation from the active side of the cell is presented in this work. Three solar cell prototypes were created and tested for efficacy, resulting in an …


Characterizations Of Eco-Friendly Class C Fly Ash-Based Alkali-Activated Mixtures For Various 3d-Printing Techniques, Fareh Abudawaba Jan 2025

Characterizations Of Eco-Friendly Class C Fly Ash-Based Alkali-Activated Mixtures For Various 3d-Printing Techniques, Fareh Abudawaba

Doctoral Dissertations

This study explored the potential of using high-calcium class C fly ash (FA) as the main precursor for synthesizing alkali-activated mortar (AAM) suitable for 3D-printed concrete (3DPC) applications. The objective was to broaden the selection of AAMs, designed to suit various printing techniques, including continuous mixing and pumping, large batch mixing, and set-on-demand processes. The study began by assessing the fresh properties of various mixtures, utilizing tests such as open time (OT), initial setting time (IST), immediate axial deformation, and penetration test (PT), to determine the mixtures' extrudability and buildability. The study optimized mixtures with a broad spectrum of cycle …


Applications Of Tetramethyl-Guanidine Supported Cationic Transition Metal Sites Towards C─N Bond Construction Methodologies And [3+2] Cycloaddition Reactions, Suraj Kumar Sahoo Jan 2025

Applications Of Tetramethyl-Guanidine Supported Cationic Transition Metal Sites Towards C─N Bond Construction Methodologies And [3+2] Cycloaddition Reactions, Suraj Kumar Sahoo

Doctoral Dissertations

"We present a family of divalent cationic bipodal and tripodal M(II) reagents (M = Mn, Fe, Co) supported by superbasic tetramethyl-guanidinyl (TMG) residue framework with applications towards C─N bond construction methodologies. These cationic reagents possess unique characteristics since their enhanced Lewis acidity facilitates in situ elaboration of the primary nitrene-transfer product (aziridine). Indeed, further aziridine-ring opening and cycloaddition of several dipolarophiles (nitriles, alkenes, ketones) permits the three-component synthesis of valuable five-membered N-heterocycles, commonly found in pharmaceuticals and agrochemicals.

We undertake a more systematic study to unravel parameters that make certain divalent metal sites more suitable as catalysts for the in-situ …


Development Of Ligands And Metal Complexes With Weakly Coordinating Apical Elements And Their Application To Nitrene Insertion And Addition To C‒H And C=C Bonds, Meenakshi Sharma Jan 2025

Development Of Ligands And Metal Complexes With Weakly Coordinating Apical Elements And Their Application To Nitrene Insertion And Addition To C‒H And C=C Bonds, Meenakshi Sharma

Doctoral Dissertations

"We present a family of triangular coinage metal M3Cl3 complexes [M = Cu (I), Ag (I)] supported by antimony [Sb (III)], and bismuth [Bi (III)]-centered highly basic tetramethyl-guanidinyl [TMG3trphen-E] (E = Sb, Bi) ligand frameworks with their applications as catalysts toward the construction of C‒N bond through aziridination and amination reaction methodologies.

The [(TMG3trphen-Sb)Cu3(µ-Cl)3] catalyst gives better yields of aziridines with styrenes than [(TMG3trphen-Bi)Cu3(µ-Cl)3] with PhINTs as a nitrene source. However, the catalytic reactivity of both catalysts is enhanced by an electrophilic nitrene, PhINTces for …