Inorganic Chemistry Commons^™

Molybdenum Alkylidyne Complexes With Phenoxide Ligands For Alkyne Metathesis, Marvin L. Stewart Jr

LSU Doctoral Dissertations

Abstract

Alkyne metathesis is a powerful synthetic tool, which provides easy access to complex organic molecules in a single-step. It is a dynamic covalent reaction that scrambles alkynes, carbon-carbon triple bonds (C≡C). Molybdenum- or tungsten-alkylidyne (Mo≡C, W≡C) complexes are typically used as catalyst to cleave and reform alkyne bonds. Our goal has been to gain a deeper understanding of the intrinsic differences between functional ligands by the development of novel phenoxide ligands.

In chapter 2 we explore the detailed synthesis of novel phenoxide podand ligands in an effort to identify their mo-alkylidyne complexes. We were able to synthesize a variety …

Chiral Recognition Of Chiral (Hetero)Cyclic Derivatives Probed By Tetraaza Macrocyclic Chiral Solvating Agents Via ¹H Nmr Spectroscopy, Yu Wang, Hongmei Zhao, Chunxia Yang, Lixia Fang, Li Zheng, Hehua Lv, Pericles Stavropoulos, Lin Ai, Jiaxin Zhang

Chemistry Faculty Research & Creative Works

In the Field of Chiral Recognition, Chiral Cyclic Organic Compounds, Especially Heterocyclic Organic Compounds, Have Attracted Little Attention and Have Been Rarely Studied as Chiral Substrates by Means of 1H NMR Spectroscopy. in This Paper, Enantiomers of Thiohydantoin Derivatives, Representing Typical Five-Membered N,N-Heterocycles, Have Been Synthesized and Utilized for Assignment of Absolute Configuration and Analysis of Enantiomeric Excess. All Enantiomers Have Been Successfully Differentiated with the Assistance of Novel Tetraaza Macrocyclic Chiral Solvating Agents (TAMCSAs) by 1H NMR Spectroscopy. Surprisingly, Unprecedented Nonequivalent Chemical Shift Values (Up to 2.052 Ppm) of the NH Proton of Substrates Have Been Observed, a New …

High Resolution Mass Spectrometry As A Platform For The Analysis Of Polyoxometalates, Their Solution Phase Dynamics, And Their Biological Interactions., Daniel T. Favre

Doctoral Dissertations

Polyoxometalates (POMs) are a class of inorganic molecule of increasing interest to the inorganic, bioinorganic and catalytic communities among many others. While their prevalence in research has increased, tools and methodologies for the analysis of their fundamental characteristics still need further development. Decavanadate (V10) specifically has been postulated to have several unique properties that have not been confirmed independently. Mass spectrometry (MS) and its ability to determine the composition of solution phase species by both mass and charge is uniquely well suited to the analysis of POMs. In this work we utilized high-resolution mass spectrometry to characterize V10 in aqueous …

Nitrene-Transfer Chemistry To C-H And C═C Bonds Mediated By Triangular Coinage Metal Platforms Supported By Triply Bridging Pnictogen Elements Sb(Iii) And Bi(Iii), Meenakshi Sharma, Reece M. Fritz, Joseph O. Adebanjo, Zhou Lu, Thomas R. Cundari, Mohammad A. Omary, Amitava Choudhury, Pericles Stavropoulos

Chemistry Faculty Research & Creative Works

Tripodal Ligands (TMG3trphen-E) That Feature Heavy Pnictogen Elements (E = Sb(III), Bi(III)) And Tetramethylguanidinyl (TMG) Arms Have Been Explored In Stabilizing Cu(I) And Ag(I) Sites And Facilitating Nitrene-Transfer Chemistry. Compounds [(TMG3trphen-E)M3(Μ-X)3] (M = Cu(I), Ag(I); X = Cl, Br, I) Have Been Generated Upon Extraction Of M3(Μ-X)3 Units From MX Sources, Exhibiting Support Of The Crown-Shaped M3(Μ-X)3 Fragment By M-NTMG Bonds And Triply Bridging E → M3 Interactions. Orbital Interactions Between Cu(I) Sites And NTMG Residues Are More Dominant Than Sb/Bi → Cu3 Donor Interactions Between The Sb 5s Or Bi 6s Orbitals And Admixed Cu 4s/3d Orbitals, With Larger …

Mechanistic Investigation Of C—C Bond Activation Of Phosphaalkynes With Pt(0) Complexes, Roberto M. Escobar, Abdurrahman C. Ateşin, Christian Müller, William D. Jones, Tülay Ateşin

Research Symposium

Carbon–carbon (C–C) bond activation has gained increased attention as a direct method for the synthesis of pharmaceuticals. Due to the thermodynamic stability and kinetic inaccessibility of the C–C bonds, however, activation of C–C bonds by homogeneous transition-metal catalysts under mild homogeneous conditions is still a challenge. Most of the systems in which the activation occurs either have aromatization or relief of ring strain as the primary driving force. The activation of unstrained C–C bonds of phosphaalkynes does not have this advantage. This study employs Density Functional Theory (DFT) calculations to elucidate Pt(0)-mediated C–CP bond activation mechanisms in phosphaalkynes. Investigating the …

Embedding Information Literacy Practices In An Upper Division Chemistry Lab Class At A University In The United States Of America, Christopher Randles, Matilynn Lamm, Katy A. Miller

Faculty Scholarship and Creative Works

This poster discusses the implementation of information literacy into an upper division inorganic chemistry lab and the strategies employed to develop students’ information literacy in the laboratory course.

Luminescent Group 11 Metal (I) Chalcogen Clusters With A Conjugated Diphosphine Ligand, Kai Yu Jeffrey Li

Electronic Thesis and Dissertation Repository

Polynuclear Au (I) complexes exhibit rich photochemical properties and have the potential to find applications as molecular sensors, switches, or energy storage devices. Although dinuclear Au (I) complexes with bridging diphosphines have been extensively examined, most of those reported do not contain rigid-diphosphine ligands.

This thesis examines how the rigid diphosphine, 4,6-bis(diphenylphosphino)dibenzofuran (DBFDP) can be incorporated for the controlled assembly of photoluminescent gold (I) metal – chalcogenolate (chalcogenolate = RS^-, RSe^-; R = organic moiety) and gold (I) chalcogenide (chalcogenide = S^2-, Se^2-) bimetallic complexes. In these studies, the chalcogen …

Exploring The Reactivity Of Metal-Ligand Cooperative Complexes With Dioxazolones, Terminal Alkynes, And 2-Ethynylbenzyl Alcohol, Megan A. Hoffer Miss

Electronic Thesis and Dissertation Repository

N-Acyl ketenimines were attempted to be synthesized catalytically by [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ with phenylacetylene and 3-phenethynyl-1,2,4-dioxazol-5-one. Trapping agents were employed to identify the major product of the reaction, as many products were formed. [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ reacts with 3-phenethynyl-1,2,4-dioxazol-5-one generating an isocyanate via the Curtius rearrangement, confirmed by a forced Curtius rearrangement with 3-phenethynyl-1,2,4-dioxazol-5-one and 1,2,4-triazole. Rates of vinylidene formation using [Ru(Cp)(P^Ph₂N^Ph₂)(NCMe)]PF₆ and various terminal alkynes of different sterics and electronics were evaluated using a Hammett analysis for and simple rate comparisons. …

Amination Of 2-Bromo-6-Methylaminopyridine, Matthew H. Elterman

Honors College Theses

Extended metal atom chains (EMACs) represent molecular structures comprising a linear arrangement of metal ions, accompanied by supporting ligands. These compounds possess intriguing properties, yet remain understudied, drawing interest from diverse fields such as physics. However, synthesizing these multimetallic complexes poses significant challenges due to their intricate nature and specificity. Bridging ligands like silyl aminopyridine (SAP) and dipyridyl amine (DAP) have been utilized successfully to support EMACs, with SAP's application in this context being limited to a single published case, highlighting the urgent need for stabilization. This project aims to address this challenge through the synthesis of a novel scaffolded …

A Comparative Study Of Cationic Copper(I) Reagents Supported By Bipodal Tetramethylguanidinyl-Containing Ligands As Nitrene-Transfer Catalysts, Suraj Kumar Sahoo, Brent Harfmann, Himanshu Bhatia, Harish Singh, Srikanth Balijapelly, Amitava Choudhury, Pericles Stavropoulos

Chemistry Faculty Research & Creative Works

The Bipodal Compounds [(TMG2biphenN-R)CuI-NCMe](PF6) (R = Me, Ar (4-CF3Ph-)) And [(TMG2biphenN-Me)CuI-I] Have Been Synthesized With Ligands That Feature A Diarylmethyl- And Triaryl-Amine Framework And Superbasic Tetramethylguanidinyl Residues (TMG). The Cationic Cu(I) Sites Mediate Catalytic Nitrene-Transfer Reactions Between The Imidoiodinane PhI = NTs (Ts = Tosyl) And A Panel Of Styrenes In MeCN, To Afford Aziridines, Demonstrating Comparable Reactivity Profiles. The Copper Reagents Have Been Further Explored To Execute C-H Amination Reactions With A Variety Of Aliphatic And Aromatic Hydrocarbons And Two Distinct Nitrene Sources PhI = NTs And PhI = NTces (Tces = 2,2,2-Trichloroethylsulfamate) In Benzene/HFIP (10:2 V/v). Good Yields …

Conversion Of Cellulose To 5-Hydroxymethylfurfural As Sustainable Energy: A Bibliometric Analysis By Vosviewer, Royyan Faradis, Ardiansyah Bagus Suryanto, Irmina Kris Murwani

Journal of Environmental Science and Sustainable Development

The developments of the global economy and society impact resources and the environment. This condition requires an alternative to find new, safe, and sustainable energy types. The conversion of cellulose to 5-hydroxymethylfurfural (5-HMF) has become a significant area of research interest. It has triggered the development of research directions related to biomass and energy because it can be an intermediary source for making polymers, solvents, pharmaceuticals, and biofuels. The primary objective of this study is to give a bibliometric analysis of 1753 reports on the development of research on cellulose conversion to 5-HMF from 1965 to 2021. The data were …

Microplate-Like Metal Pyrophosphate Engineered On Ni-Foam Towards Multifunctional Electrode Material For Energy Conversion And Storage, Rishabh Srivastava

Electronic Theses & Dissertations

High clean energy demand, dire need for sustainable development, and low carbon footprints are the few intuitive challenges, leading researchers to aim for research and development for high-performance energy devices. The development of materials used in energy devices is currently focused on enhancing the performance, electronic properties, and durability of devices. Tunning the attributes of transition metals using pyrophosphate (P₂O₇) ligand moieties can be a promising approach to meet the requirements of energy devices such as water electrolyzers and supercapacitors, although such a material’s configuration is rarely exposed for this purpose of study.

Herein, we grow …

Enhanced Mechanical Strength Of Soybean Oil-Based Non-Isocyanate Polyurethane Adhesive For Wood Application By Introducing Nanofillers, Vatsal Chaudhari

Electronic Theses & Dissertations

Polyurethane (PU) is a versatile material that finds extensive use in various industries including bedding, construction, automotive, and packaging. Historically, this particular polymer relied significantly on petrochemical resources, a practice that was considered to have negative environmental impacts. The conventional method for preparing PU involves the use of isocyanate, which is a disadvantage due to its negative impact on the environment and human health. The resolution of this problem entails identifying an appropriate substitute for petroleum-derived products that minimize their impact on both the environment and human health. The researchers earlier utilized soybean oil, for the formulation of PUs in …

Optimization Of Transition-Metal Inclusive Carbon Aerogels For Electrochemical Energy Applications, Allen Dalton Davis

Electronic Theses & Dissertations

The ever-growing need for energy alongside rising concerns for climate change demands the development of renewable energy technologies. Hydrogen fuel cells are a promising technology that can serve to either supplement energy generation or act as a lone power source. Yet for these devices to be truly green, the hydrogen that serves as fuel must be procured from a renewable resource. Electrolytic water splitting is a process that allows for the dissociation of water into H₂ and O₂. For this process to be practical, the electrolyzer needs to demonstrate high efficiency and stability, as well as a …

Exploring Soybean Oil-Based Polyol And Effect Of Non-Halogenated Flame Retardants In Rigid Polyurethane Foam, Sahithi Kondaveeti

Electronic Theses & Dissertations

To address the increasing demand for sustainable biomaterials due to the depletion of fossil fuel resources and growing environmental concerns, a new type of biodegradable and environmentally friendly rigid polyurethane foam (RPUF) has been synthesized. These foams are derived from chemically modified soybean oil-based polyol obtained from soybean oil by epoxidation followed by a ring-opening reaction. Polyurethane foam is generally used in construction, furniture, and automobile industries but is highly flammable and releases toxic gases and smoke during combustion. In this study, a highly efficient synergistic effect halogen-free flame-retardant (FR) melamine salt, 2-carboxyethyl(phenyl)phosphinic acid melamine salt (CMA) was synthesized from …

Hydrothermal Synthesis Of First-Row Transition Metal Polyanions Towards The Design Of Frustrated Magnetic Materials, Megan Smart

All Dissertations

Novel modern materials are constantly being discovered as humanity seeks constantly better improvement to the optics and electronics around us, from lasers used in medical therapies to the magnets and supercomputing chips in our phones. Inorganic oxides commonly draw inspiration from naturally occurring minerals to template new discoveries through substitution of similarly behaving elements with the goal of inducing certain desired properties, such as ferroelectricity or creating the elusive quantum spin liquid. While many minerals are silicates, its periodic table neighbor germanium(IV) has a rich and under-explored crystal chemistry that could contain many new structures and magnetic materials. Another common …

Sterically Encumbering Ligands For The Synthesis And Stabilization Of Iron Nitride And Iron Oxo Compounds, Asiel Mena

Open Access Theses & Dissertations

The study of iron-nitrides has been found to be very attractive due to their potential role in processes like Haber-Bosch and nitrogen fixation by nitrogenase. The role of iron-nitrides in these processes is yet not well understood, and the fact that only handful of terminal iron-nitrides have been isolated or spectroscopically detected motivates us to study this type of systems, since much remains to be learned about the electronic and structural factors that affect the chemistry of the Feâ?¡N bond. Recently in our group, by using a super-bulky guanidinate ligand (LAr*), the obtention of an iron-nitride ([LAr*]FeN(py) (LAr* = (Ar*N)2C(NCtBu2), …

Scalable Solution Processing Of Niox Nanoparticles., Peter James Armstrong

Electronic Theses and Dissertations

Perovskite solar cells (PSCs) are a promising alternative to silicon-based photovoltaics. However, PSCs face several challenges due to shortcomings in their stability, module efficiency, and scaled production. Although PSCs is still a young field of research, significant attention has been given to demonstrating power conversion efficiencies that are on par with traditional silicon. With that target reached, converting the laboratory demonstration into practical materials to increase access and abundance of solar energy are among the next large targets for the field. This comes with material challenges for perovskite and their companion charge transport layers (CTLs). Among the charge transport materials …

Antibacterial Testing On Silver/Zinc Oxide Nanoparticles/Organoclay Reinforced Chitosan Biocomposites, Lisna Junaeni Muiz, Ariadne Lakshmidevi Juwono, Zulkarnaen Paputungan, Yuni Krisyuningsih Krisnandi

Makara Journal of Science

Herein, bionanocomposites of chitosan (CS)/silver nanoparticle/organoclay/zinc oxide nanoparticle (CS/Ag/OC/ZnO) were prepared for antibacterial food packaging. This study examines the time variation in the AgNP synthesis method by comparing local (74˗85% deacetylated) and commercial chitosan (75%˗85% deacetylated) as a reducing and capping agent and seeks to reconstruct the optimum ratio formulations of AgNPs and ZnONPs in bionanocomposites for food packaging. The results reveal that the synthesis of AgNPs was successfully carried out using a local chitosan solution as a reducing and capping agent. The CS/Ag/OC/ZnO films exhibit structural, mechanical, and optical properties suitable for food packaging and antibacterial activity on Staphylococcus …

Characterization And Electrolysis Of Zn And Cu 2,6-Diacetylpyridine Bis(2-Hydrazinopyridine), Bailee G. Duff, Christine Phipps, Craig Grapperhaus

The Cardinal Edge

With increasing demands for fuel and concerns over climate change, the search for sustainable energy sources is ever growing. Hydrogen is a potential solution to these issues, as it is clean, recyclable, and efficient. However, hydrogen must be generated, unlike other fuel sources that are naturally ready for use. The most sustainable method for hydrogen production involves water electrolysis, as no pollution is generated. The water splitting process contains a cathodic hydrogen evolution reaction (HER) and an anodic oxygen evolution reaction (OER). These reactions require a catalyst to overcome the kinetic barrier present and meet the high voltage requirements for …