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Articles 1 - 14 of 14
Full-Text Articles in Inorganic Chemistry
Understanding The Binding Of Nickel(Ii) Bromide To A Zirconium Metal-Organic Cage For Heterogeneous Catalysis, Luci Green
Caroliniana Undergraduate Research Journal
Heterogeneous catalysts offer inherent advantages in improving the sustainability of industrial chemical processes. Their high ease of separation and recyclability has the potential to reduce the cost, waste, and energy consumption of processes that currently rely on homogeneous catalysts. Metal–organic cages (MOCs) are an attractive material for heterogeneous catalysis due to their discrete and highly tunable structures, which can be functionalized by binding these complexes with catalytically active metals. The specific objective of this study is to provide preliminary insight into the binding of nickel(II) bromide (NiBr2) to zirconium MOCs, which was done by studying the binding of …
Designing Surface-Induced Entatic States In Copper Complexes For Tunable Reactivity, Rachel Kiser
Designing Surface-Induced Entatic States In Copper Complexes For Tunable Reactivity, Rachel Kiser
Senior Theses
Copper catalysts play an important role in electrocatalytic oxidation reactions due to their redox flexibility and relative abundance compared to noble metal catalysts. In biological systems, copper metalloenzymes often achieve enhanced reactivity through an entatic state. Entasis is described as an active site or metal center being constrained to a geometric and electronic state, minimizing primary sphere reorganization energy and achieving higher rates of electron transfer. This study investigates whether entasis can be achieved in synthetic molecular catalysts by immobilizing Cu(I) complexes onto metal oxide surfaces. Two Cu(I) complexes bearing carboxylate-functionalized ligands were examined both in homogeneous solution and when …
Exploring Inorganic And Organometallic Chemistry, W. Christopher Boyd Phd
Exploring Inorganic And Organometallic Chemistry, W. Christopher Boyd Phd
MSL Academic Endeavors eBooks
This textbook, Exploring Inorganic and Organometallic Chemistry, covers the fundamentals of inorganic and organometallic chemistry for undergraduate and graduate students. Both theories of structure and bonding and reaction chemistry are covered, with applications to the catalysis of organic reactions, biochemistry, and drug design. A modular approach allows for basic materials of each chapter to be covered in an undergraduate course, with more advanced material suitable for M.S. and Ph.D. students."
Synthesis, Electrical Conductivity, Electrocatalytic Activity For Water Splitting, And Pseudocapacitive Properties Of Perovskite Oxide Derivatives., Kinithi Meththa Kumari Wickramaratne
Synthesis, Electrical Conductivity, Electrocatalytic Activity For Water Splitting, And Pseudocapacitive Properties Of Perovskite Oxide Derivatives., Kinithi Meththa Kumari Wickramaratne
Electronic Theses and Dissertations
Developing green and sustainable energy solutions is crucial to addressing the energy and environmental challenges. Hydrogen is an attractive candidate given its high energy density and low carbon emission compared to gasoline and coal. Electrochemical water splitting through a water electrolyzer is recognized as a green method for generating hydrogen and oxygen gases. Developing cost-effective electrocatalysts to reduce overpotential in hydrogen and oxygen generation is essential for the overall process. The growing interest in perovskite oxides as versatile and sustainable catalysts is driven by their compositional flexibility, tunable electronic structure, earth abundance, and inherent catalytic performance. In our research, we …
Synthesis And Characterization Of Silver(I) And Manganese(Ii) Complexes With Thione Imidazoles, Shannon Keyser, Audrey Lawrence, Jaime M. Murphy Ph.D.
Synthesis And Characterization Of Silver(I) And Manganese(Ii) Complexes With Thione Imidazoles, Shannon Keyser, Audrey Lawrence, Jaime M. Murphy Ph.D.
Honors Theses
Coordination polymers are chemical complexes with versatile applications such as catalysts, electrical conduc-tors, non-linear optics, magnetics, chemical sensing, and molecular storage. The polymers are comprised of a repeating series of metal-ligand complexes, which form various structures in varying ratios depending on the metal and ligand used. Certain metal-ligand combinations have shown particular promise as potentially being polymers or, if not polymers, possessing other useful features such as electromagnetic conductivity. Complexes were synthesized using silver(I) and manganese(II) with the ligands methimazole, 2-mercaptoimidazole, and thiocarbanilide with counterions of either chloride or nitrate. These com-plexes were characterized using elemental analysis, infrared spectroscopy, and …
Synthesis Of Trisubstituted Bismuth Complexes For Future Research, Cassidy Belk
Synthesis Of Trisubstituted Bismuth Complexes For Future Research, Cassidy Belk
Undergraduate Theses
Bismuth, a relatively inexpensive heavy metal with low toxicity, has the potential to be used in medicines and anticancer drugs. This project is exploring bismuth complexes with ligands based on chalcones, which are a type of small organic molecules with known anticancer properties. Preliminary results on a bismuth-chalcone complex indicate that substituted aryl bismuth complexes have better anticancer activity than triphenylbismuth or the chalcone ligand on its own. A series of trisubstituted bismuth molecules were synthesized using a BiCl3 Grignard reaction under a nitrogen atmosphere with different substituents to provide electron donating groups, electron withdrawing groups or bulk. X-ray …
Amination Of 2-Bromo-6-Methylaminopyridine, Matthew H. Elterman
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 …
Hydrothermal Synthesis Of First-Row Transition Metal Polyanions Towards The Design Of Frustrated Magnetic Materials, Megan Smart
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 …
Synthesis And Characterization Of Redox-Noninnocent Pyrazine(Diimine) Iron Complexes And An Inverted Pyridine(Diimine) Ligand, Jaylan Billups
Synthesis And Characterization Of Redox-Noninnocent Pyrazine(Diimine) Iron Complexes And An Inverted Pyridine(Diimine) Ligand, Jaylan Billups
Theses and Dissertations
Cooperativity between the metal center and the ligand has been shown in nature to be an important feature of systems that catalyze two-electron processes that first-row transition metals usually cannot catalyze on their own. In these cases, the ligand acts as a site of reactivity that in many instances can store electrons or react directly with substrates in solution. The design and study of systems where there is synergy between the metal and the ligand have been leveraged to catalyze polymerization and hydrogenation-type reactions as well as the activation of small molecules such as dihydrogen. Specifically, the pyridine(diimine) ligand scaffold …
A Comparative Study Of Two Nickel-Based Suzuki-Miyaura Hybrid Molecular Catalysts, Mollie Morrow
A Comparative Study Of Two Nickel-Based Suzuki-Miyaura Hybrid Molecular Catalysts, Mollie Morrow
Senior Theses
Two molecular nickel-based catalysts, (2,2’bipyridine-4,4’-carboxylic acid)nickel(II) chloride and (2,2'-bipyridine-4,4'-diamidopropylsilatrane)nickel(II) chloride, were synthesized and subsequently attached to a solid support in the form of amorphous silicon dioxide to create two hybrid molecular/heterogeneous catalysts. Characterization using ICP-MS and ATR-FTIR confirms that both catalysts are bonded to the SiO2 support. The catalysts were both able to catalyze a Suzuki-Miyarua cross-coupling which their molecular counterparts were unable to; the carboxylate catalyst was able to achieve yields of 10% and the silatrane catalyst achieved yields of up to 50%. Post-reaction analysis indicated that while some catalyst desorption occurred in both complexes, active catalytic species …
Dirhenium Compounds Containing The Diphosphine Ligands Ph2pch2pph2, Ph2pch(Cn)Pph2, Or Ph2pch(Ch3)Pph2: A Comparative Study, Hannah C. Arthur
Dirhenium Compounds Containing The Diphosphine Ligands Ph2pch2pph2, Ph2pch(Cn)Pph2, Or Ph2pch(Ch3)Pph2: A Comparative Study, Hannah C. Arthur
Undergraduate Honors Theses
When M2L10 complexes containing two rhenium(III) atoms in a quadruple bond react with an excess of the diphosphine ligand Ph2PCH2PPh2, the bond order decreases, and the rhenium is reduced to rhenium(II). When two diphosphine ligands are bonded to the dirhenium center, they can adopt a trans-trans, trans-cis, or cis-cis configuration. NMR spectra of compounds that adopt the cis-cis arrangement show unusually large downfield shifts for one of the bridgehead methylene hydrogens (P-CH2-P). To understand the unusual chemical shift, the hydrogens first have to be assigned. The strategy for …
The Utilization Of Metal-Ligand Cooperativity For Electrocatalytic Reduction And Catalytic Hydration., Steven Cronin
The Utilization Of Metal-Ligand Cooperativity For Electrocatalytic Reduction And Catalytic Hydration., Steven Cronin
Electronic Theses and Dissertations
Small molecules are building blocks for developing larger materials. These small molecules could be extremely small, such as hydrogen, or larger such as a nitrile, but their impact on the global economy is massive. This dissertation describes a catalyst for three reactions involving small molecules; 1) the hydrogen evolution reaction, 2) the carbon dioxide reduction reaction, 3) nitrile hydration. The catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) use “metal-ligand cooperativity” between the Lewis acid Zn(II) metal ion and an uncoordinated Lewis base nitrogen in the ligand framework to activate substrates. The complex has been analyzed via NMR, UV/Vis, single crystal X-ray crystallography, …
Electro- And Photocatalytic Carbon Dioxide Reduction And Thermal Isomerization Of Highly Strained Tricyclocompounds, Weiwei Yang
Electro- And Photocatalytic Carbon Dioxide Reduction And Thermal Isomerization Of Highly Strained Tricyclocompounds, Weiwei Yang
Electronic Theses and Dissertations
Anthracene-bridged dinuclear rhenium complexes are reported for electrocatalytic and photocatalytic carbon dioxide (CO2) reduction to carbon monoxide (CO). Related by hindered rotation of each rhenium active site to either side of the anthracene bridge cis and trans conformers have been isolated and characterized. Electrochemical studies reveal distinct mechanisms whereby the cis conformer operates via cooperative bimetallic CO2 activation and conversion and the trans conformer reduces CO2 through well-established single-site and bimolecular pathways analogous to Re(bpy)(CO)3Cl. Higher turnover frequencies are observed for the cis conformer (35.3 s−1) relative to the trans conformer (22.9 s−1) with both outperforming Re(bpy)(CO)3Cl (11.1 s−1). Photocatalytic …
The Investigation Of Protonation Of [Mo2(Nto)2(S2p(Oet)2)2(So)(Sbn)(O2cme)]., Adria Schwarber
The Investigation Of Protonation Of [Mo2(Nto)2(S2p(Oet)2)2(So)(Sbn)(O2cme)]., Adria Schwarber
College of Arts & Sciences Senior Theses
No abstract provided.