Inorganic Chemistry Commons^™

Transition Metal Complexes With Reactive Trimethylsilylchalcogenolate Ligands: Precursors For The Preparation Of Ternary Nanoclusters, Chhatra Bahadur Khadka

Electronic Thesis and Dissertation Repository

The Co²⁺ and Mn²⁺ complexes (N,N´-tmeda)Co(ESiMe₃)₂ (E = S, 1a; E = Se, 1b), (3,5-Me₂C₅H₃N)₂Co(ESiMe₃)₂ (E = S, 2a; E = Se, 2b), [Li(N,N´-tmeda)]₂[(N,N´-tmeda)Mn₅(μ-ESiMe₃)₂(ESiMe₃)₄(μ₄-E)(μ₃-E)₂] (E = S, 3a; E = Se, 3b), [Li(N,N´-tmeda)]₂[Mn(SSiMe₃)₄] (4), [Li(N,N´-tmeda)]4[Mn₄(SeSiMe₃)₄(μ_{3 …}

Targeted Synthesis And Characterization Of Nanostructured Silicate Building Block Supports And Heterogeneous Catalysts With Tungsten(Vi) Or Zirconium(Iv) Centers, Michael Edward Peretich

Doctoral Dissertations

Catalysts play a vital role in almost every aspect of our lives and are used in the production of fuels, polymers, chemicals, foods, and pharmaceuticals. One challenge facing the heterogeneous catalysis community is the targeted synthesis of dispersed catalyst ensembles.

The Barnes research group has developed a general methodology for the synthesis of nanostructured silicate building block supports and heterogeneous catalysts. This methodology provides researchers with the ability to control the dispersion of surface functionality, the dispersion of metal cation centers, the number of linkages from the metal cation center to the support, the surface area of the support, and …

Synthesis Of An Antimicrobial Textile Coating, William M. Morris

Chemistry and Biochemistry

A titania nanosol was synthesized and coated onto nylon/cotton blended textile substrates. The substrates were characterized via SEM for adhesion and nanoparticle formation, then subjected to antimicrobial efficacy tests. The titania nanosol was successfully coated on to textiles samples. Particles were observed to be around 2 by 3 micrometers and formed between the interstitial space of textile fibers. Although larger than typical nanoparticles, the coatings exhibited what seemed to be antimicrobial activity. Titania nanosol coated textile samples were subjected to Kirby Bauer Assay in the presence of S. aureus. The coated textile sample exhibited an inhibition of growth around its …

Electrochemistry Of Pani/Metal Composites In Basic Solutions, Tamthinhan Quy

UNLV Theses, Dissertations, Professional Papers, and Capstones

Polyaniline (PANI) has been extensively investigated due to its unique conductivity, which is primarily dependent on the oxidation state of the material and the solution pH. PANI is an insulator when it is oxidized, and the solution pH exceeds four. Numerous attempts to extend PANI's conductivity to neutral and alkaline environments have been unsuccessful. However, our previous study has demonstrated that PANI/Pd composite is conductive and catalytically active in a basic solution, pH ∼ 12. Therefore, the conductivity and the electrochemical properties of PANI composites including PANI/Au, PANI/Pd and PANI/Pt were evaluated in basic solutions. The fundamental studies of PANI/metal …

Reactivity Of Dimethylplatinum (Ii) Complexes, Muhieddine A. Safa

Electronic Thesis and Dissertation Repository

This thesis describes a study of dimethylplatinum(II) and dimethylplatinum(IV) complexes containing bidentate nitrogen donor ligands. This work deals with oxidative addition, and reductive elimination chemistry, and it focuses on synthesis, characterization, and reaction mechanisms in studies of these complexes.

The compound [PtMe₂(bpe)], bpe = 1,2-bis(2-pyridyl)ethane, is easily oxidized to give octahedral organoplatinum(IV) complexes and the subsequent chemistry is profoundly influenced by the accompanying strain induced in the 7-membered Pt(bpe) chelate ring. On reaction of [PtMe₂(bpe)] with HCl, the initial product [PtHClMe₂(bpe)] undergoes reductive elimination of methane to form [PtClMe(bpe)]. In contrast, methyl …

Computational Studies Of Ion Transport In Polymer Electrolytes, Hui Wu

Doctoral Dissertations

Improving ionic conductivity and lithium mobility in polymer electrolytes is important for their practical use for battery electrolytes. In this study, a combination of molecular dynamics and Monte Carlo simulations was used to bring insight into lithium ion transport in poly(ethylene oxide) (PEO) with plasticizers and also next to alumina solid surface doped with lithium salt. The simulations were performed using a moderately high molecular weight polymer (Mn = 10,000 g/mol) at an EO:Li ratio of 15. For the plasticized system, the PEO with LiN(CF3SO 2)2 (LiTFSI) was mixed with 10 wt% plasticizers that included either cyclic ethylene carbonate …

Uncovering New Bonding Motifs: The Synthesis Of Chalcogen And Phosphorus Complexes Supported By Nitrogen Based Ligands, Caleb D. Martin

Electronic Thesis and Dissertation Repository

The chemistry of the main group elements with nitrogen based ligands has been an area that has received little attention in comparison to transition metals. The preliminary investigations have focused on groups 13 and 14 revealing new bonding motifs and interesting reactivity. This has motivated us to synthesize group 15 and 16 derivatives in new bonding arrangements capable of activating small molecules.

In pursuit of isolating such species, the reactivity of sulfur dichloride and “S(OTf)2” with a series of diazabutadiene (DAB) ligands was explored. The substitution on the ligand was extremely influential on the outcome of the reaction. Alkyl groups …

Quenching Of The Fluorescence Of Tris (2 2-Bipyridine) Ruthenium(Ii) [Ru(Bipy)3]2+ By A Dimeric Copper(Ii) Complex., Kevin E. Cummins

Electronic Theses and Dissertations

The quenching of the [Ru(bipy)₃]²⁺ by Cu₂L²⁺ was studied and the data were plotted with the Stern-Volmer equation. The plot showed a break and was divided into 2 regions, <0.5 and >0.5 Cu₂L²⁺: [Ru(bipy)₃]²⁺ molar ratio. Quenching above the 0.5 Cu₂L²⁺: [Ru(bipy)₃]²⁺ molar ratio was slower (330 x 10^-6 M^-1s^-1) than the quenching rate reaction below 0.5 ratio (387 x 10^-6 M^-1s^-1).

With Cu₂L²⁺ being a dimeric complex the …

Solid-State Synthesis Of Imide Ligands For The Self-Assembly Of Metal-Organic Materials, Jason Alexander Perman

USF Tampa Graduate Theses and Dissertations

In this research project, reduction or complete elimination of organic solvents is explored in the synthesis of cyclic imides using a technique that brings reagents into favorable position to react. Cocrystal Controlled Solid-State Synthesis (C³S^y3), takes advantage of supramolecular interactions such as hydrogen bonding and π-π stacking to form a cocrystal which can sequential be heated to complete the condensation reaction and produce a desirable product. Twenty-five successful condensation reactions result in high and clean yield.

C³S^y3 of cyclic imides with auxiliary hydrogen bonding moieties like carboxylic acid, carboxylate or pyridyl groups are …

Synthetic And Mechanistic Studies Of Coupling Reactions Involving C-H Bond Activation, Ki Hyeok Kwon

Dissertations (1934 -)

Transition metal-catalyzed C-C bond forming reactions involving C-H bond activation have been shown to be effective methods for functionalization of unreactive compounds. Since Murai's pioneering work on ruthenium-catalyzed regioselective arene-to-alkene coupling reactions, a number of well-defined, late transition metal catalysts have been shown to mediate regioseletive C-C bond forming reaction involving C-H bond activation. Recently, late transition metal complexes have also been found to catalyze the regioselective coupling reaction of nitrogen containing compounds with alkenes as well as sp3 bond insertions and oxidative coupling reaction of aimdes. The catalytic C-C bond forming reaction involving C-H bond activation would provide simple …

Exploring The Chemistry Of Cyclopentadienyl-Cobalt-Cyclobutadiene (Cpcocb) Complexes And Synthesis Of Side-Chain Cpcocb Polymers, Preeti Chadha

Electronic Thesis and Dissertation Repository

Synthetic metallopolymers have acquired ample attention recently due to their potential applications as precursors to functional soft materials. Organometallic polymers combine the best of both organic and inorganic polymers. Polyferrocenes comprise the major portion of organometallic polymers. Therefore, quest for new monomeric precursors to organometallic polymers has expediated. One efficient method for obtaining main-chain metallopolymers is by the ring opening polymerization (ROP) of strained cyclic metallacylophanes(MCPs). Organometallic polymers containing cyclopentadienyl-cobalt-cyclobutadiene (CpCoCb) have been targeted since early 1990’s due to their isoelectronic nature (cf. ferrocene) with three major groups working in this area. The early CpCoCb containing polymers were prepared …

Part A: The Use Of Nonionic Associative Polymers For The Thickening And Emulsifying Of Personal Care Products/ Part B: The Synthesis Of A Manganese Sod Mimetic For Reactive Coatings, Mallory Lynn Mcmahon

Master's Theses

Part A

The use of nonionic associative thickeners was proposed for personal care applications. Various limitations of current rheology modifiers used in personal care were discussed. Nonionic associative polymers were examined as both thickeners and emulsifiers. The structure/property relationship for nonionic polymers and their ability to thicken and emulsify were fully examined. Results showed an increase in thickening efficiency for nonionic associative polymers with higher log(P) (partition coefficient) values. This was due to the formation of smaller aggregates and increased bridging between aggregates. The connection between oil polarity, log(P) of the associative polymer, and emulsion stability showed no relationship however; …

Targeted Synthesis And Characterization Of Isolated Zirconium (Iv) Centers In A Silicate Building Block Matrix, Katherine P. Sharp

Chancellor’s Honors Program Projects

No abstract provided.

Extraction Chromatographic Studies Of Rutherfordium And Dubnium Homologs, Megan E. Bennett

UNLV Theses, Dissertations, Professional Papers, and Capstones

Studying the chemistry of transactinide elements does not only allow for these elements to be properly placed in the Periodic Table, but it also permits for the extrapolation of the electronic structure based upon the position of the element in the Periodic Table. In addition it enable for the assessment of the role that relativistic effects play in the chemical behavior of the heaviest elements. An improved understanding of the role of relativistic effects in chemistry of the heaviest elements allows for a better understanding of the fundamentals principles that govern the Periodic Table. In order to investigate the chemistry …

Synthesis And Characterization Of Extended Solids Containing Nano-Sized Transition Metal Oxide Lattices, Matthew Williams

All Dissertations

In this research, focus has been placed on the study of magnetic anomalies due to geometric frustration of magnetic ions. The goal of the study presented in this dissertation was to synthesize pseudo&ndashlow&ndashdimensional (PLD) compounds, those structures showing zero (dot), one (chain), and two (sheet) dimensional lattices observed in extended (3D) host frameworks with enhanced anisotropic physical properties, in an attempt to elucidate some structure&ndashproperty correlations arising from magnetic spin confinement. The scope of this research involved 1) exploratory synthesis of novel, low&ndashdimensional transition metal oxide lattices, specifically Mn and V, embedded in non&ndashmagnetic oxyanion frameworks, either Ge, P, or …

A Three Dimensional Green's Function Solution Technique For The Transport Of Heavy Ions In Laboratory And Space, Candice Rockell Gerstner

Mathematics & Statistics Theses & Dissertations

In the future, astronauts will be sent into space for longer durations of time compared to previous missions. The increased risk of exposure to ionizing radiation, such as Galactic Cosmic Rays and Solar Particle Events, is of great concern. Consequently, steps must be taken to ensure astronaut safety by providing adequate shielding. The shielding and exposure of space travelers is controlled by the transport properties of the radiation through the spacecraft, its onboard systems and the bodies of the individuals themselves. Meeting the challenge of future space programs will therefore require accurate and efficient methods for performing radiation transport calculations …

Computational Investigation Of The Bioactive Selenium Compounds Ebselen And Selenious Acid, Sonia Antony

Chemistry & Biochemistry Theses & Dissertations

Selenium, a toxic element, is required in trace quantities for the proper functioning of biological systems. The experimental mechanistic study of the reactions of ebselen and selenious acid is difficult due to complexity of the reaction mixtures and the presence of short-lived intermediates. Computational modeling of the reactivity of these species can give us an insight into their mechanisms, but the process is complicated by proton exchanges associated with the mechanistic steps. In gas phase modeling, this may be corrected to a certain level using the solvent assisted proton exchange (SAPE) method. SAPE is a modeling technique that mimics solvent …

Synthesis Of N-Acetyl And C-Tert-Butyl Natural Amino Acid Substrates That Mimic Residues Of Polypeptides And Their Reactivity With [Feiv(O)(N4py)]2+: Kinetic And Mechanistic Investigations, Ashley Ann Campanali

Wayne State University Dissertations

This dissertation is divided into two chapters, the first chapter includes an introduction to reactive oxygen species and their reactions with proteins. The introduction also covers metal-based oxidants, including both heme and non-heme enzymes that activate dioxygen as well as complexes that mimic these enzymes. The work discussed in chapter one concerns the synthesis of amino acid substrates that mimic amino acid residues. Substrates synthesized were derived from Gln, Asn, Ile, Cys and Tyr. Once synthesized, these substrates were reacted with [FeIV(O)(N4Py)]2+ under pseudo-first order conditions. The mechanisms for the reactions of the most reactive substrates were investigated. Electron-transfer proton-transfer …

Supramolecular Organization Of Nanoparticles, Brenda M. Porta Linnell

Open Access Theses & Dissertations

The study of supramolecular structures with nano-architectures has become an active area of research in recent years. They have the potential to generate functional materials with applications in medicine and emerging technologies. In this dissertation, the supramolecular organization of gold nanoparticles (AuNP) and other nano-scale structures such as discrete styrene-based polymers was investigated. The synthesis and characterization of metal-mediated AuNPs systems using pendant ligands on the AuNP such as 11-diethylenetriamine-undecane-1-thiol, 11-Mercapto-undecanoic acid [2-(2-amino-ethylamino)-ethyl]-amide, Bis(11-oxo-nicotinic acid, undecine)disulfide, and 11-mercaptoundecanoic acid, and using Cu(II) to mediate the formation of supramolecular AuNP systems with sizes of 200 nm ¡V 3 fÃ?m, are …

Crystal Engineering Of Pharmaceutical Cocrystals, Sreya Mukherjee

USF Tampa Graduate Theses and Dissertations

Pharmaceutical cocrystals use principles of crystal engineering for the design of crystalline forms of drugs and can improve their solubility, bioavailability, stability and other important properties without changing the efficacy of the drug. Herein reported are pharmaceutical cocrystals of two API's, caffeine and Pentoxifylline.

Research has indicated that caffeine has the ability to reverse AB; plaque deposition in the brain (believed to be the primary cause of Alzheimer's pathogenesis) and thus revert memory and improve cognitive impairment. But owing to the fast absorption rate and short half life, a controlled release formulation of caffeine would be clinically beneficial. Thus, novel …

Investigation Of Hg(Ii) Solution Speciation By Esi-Ms And Proton Nmr, Madeline R. Nestor

Dissertations, Theses, and Masters Projects

No abstract provided.

Developing Dimetal Paddlewheel Complexes For Catalytic Applications, Margaret E. Napier

Legacy Theses & Dissertations (2009 - 2024)

Although there are countless examples of rhodium-catalyzed organic reactions in the chemical literature, the field continues to develop at a steady pace, as focus shifts taking advantage of economy of resources while maintaining efficiency of the catalytic reactions. The work presented is separated into three chapters, with each describing a specific approach to the development of new materials which can provide either a direct economy of resources and reagents or can be used for heterogenization of catalytic systems.