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Full-Text Articles in Chemistry

Fabrication Of Silver Nanoparticles In Poly (N-Isopropylacrylamide-Co-Allylacetic Acid) Microgels For Catalytic Reduction Of Nitroarenes, Zahoor Hussain Farooqi, Naghza Tariq, Robina Begum, Shanza Rauf Khan, Zafar Iqbal, Abbas Khan Jan 2015

Fabrication Of Silver Nanoparticles In Poly (N-Isopropylacrylamide-Co-Allylacetic Acid) Microgels For Catalytic Reduction Of Nitroarenes, Zahoor Hussain Farooqi, Naghza Tariq, Robina Begum, Shanza Rauf Khan, Zafar Iqbal, Abbas Khan

Turkish Journal of Chemistry

Poly(N-isopropylacrylamide-co-allyl acetic acid) [p(NIPAM-co-AAAc)] microgels were synthesized in aqueous medium by free radical emulsion polymerization using N-isopropylacrylamide as monomer, allylacetic acid as comonomer, and N,N-methylene-bis-acrylamide as cross-linker. Silver nanoparticles were fabricated inside the microgels by in situ reduction of silver ions. Microgels were analyzed by UV-visible spectroscopy, FTIR, XRD, TEM, and DLS. The formation of silver nanoparticles was confirmed by UV-visible spectroscopy. UV-visible spectra of the Ag-poly(N-isopropylacrylamide-co-allyl acetic acid) hybrid microgels showed a prominent absorption peak at about 411 nm. This peak was due to the surface plasmon resonance effect of silver nanoparticles. The hybrid microgels were used as catalyst …


Synthesis Of New Thiol-Derivatized Aminophosphines And Their Catalytic Activities In C--C Coupling Reactions, Nermi̇n Bi̇ri̇ci̇k, Nermi̇n Meri̇ç, Cezmi̇ Kayan, Zeynep Özgen, Sevi̇l Şeker Azi̇zoğlu, Bahatti̇n Gümgüm Jan 2015

Synthesis Of New Thiol-Derivatized Aminophosphines And Their Catalytic Activities In C--C Coupling Reactions, Nermi̇n Bi̇ri̇ci̇k, Nermi̇n Meri̇ç, Cezmi̇ Kayan, Zeynep Özgen, Sevi̇l Şeker Azi̇zoğlu, Bahatti̇n Gümgüm

Turkish Journal of Chemistry

A series of new aminophosphines [Ph$_{2}$PHN-C$_{6}$H$_{4}$-R, where R = $o$-SH (4a), $m$-SH (4b) or $p$-SH (4c)] were readily synthesized from cheap starting materials by the phosphorylation reaction of $o$, $m$, and $p$-aminothiophenols with Ph$_{2}$PCl in the presence of triethyl amine. The new compounds were characterized by NMR and IR spectroscopy and microanalysis. In addition, aminophosphine ligands-palladium systems were investigated as precatalysts in C-C coupling reactions. Compounds 4b and 4c were proved to be excellent catalysts for Suzuki and Heck cross-coupling reactions.


Investigating The Synthesis Of Heterocycles Via Gold Catalyzed Cyclizations And Cyclo-Dehydrating Reactions, Katherine L. Childers Jan 2015

Investigating The Synthesis Of Heterocycles Via Gold Catalyzed Cyclizations And Cyclo-Dehydrating Reactions, Katherine L. Childers

Undergraduate Honors Thesis Projects

The goal of this project was to study novel synthetic procedures for heterocycles. This was achieved through a two-part investigation. In the first part, a variety of conditions for the gold catalyzed cyclization of allenes were studied. This work was focused on the lesser studied intermolecular reactions of allenes. A variety of allenes were synthesized, and then reacted with 1,3-dipoles and a gold catalyst. These reactions were determined to be unsuccessful through the analysis of nuclear magnetic resonance spectroscopy data. In the second part of this study, the synthesis of 1,3,4-oxadiazoles was investigated. Several cited procedures were examined to determine …


Theoretical Studies Of Transition Metal Catalysis, Ryan S. Johnson Sep 2014

Theoretical Studies Of Transition Metal Catalysis, Ryan S. Johnson

Chemistry and Chemical Biology ETDs

Transition metal catalysis, being critical to nearly all aspects of the modern industrial world, is the focus of a series of theoretical studies which seek to elucidate the fundamental and electronic origins of enhanced chemical activity and selectivity. The application of density functional theory on extended single metal and alloyed surfaces, supported single metal atoms, and gas phase cationic species illuminate various aspects of transition metal catalysis in a wide range of enviornments. Adsorption, reactivity, and other mechanistic details developed here suggest possible mechanisms used to aid interpretation of experimental results and guide developement of future catalysts.


The Critical Role Of Water At The Gold-Titania Interface In Catalytic Co Oxidation, Johnny Saavedra, H. Doan, Christopher J. Pursell, L. C. Grabow, Bert D. Chandler Sep 2014

The Critical Role Of Water At The Gold-Titania Interface In Catalytic Co Oxidation, Johnny Saavedra, H. Doan, Christopher J. Pursell, L. C. Grabow, Bert D. Chandler

Chemistry Faculty Research

We provide direct evidence of a water-mediated reaction mechanism for room-temperature CO oxidation over Au/TiO2 catalysts. A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bond breaking in the rate-determining step. Kinetics and in situ infrared spectroscopy experiments showed that the coverage of weakly adsorbed water on TiO2 largely determines catalyst activity by changing the number of active sites. Density functional theory calculations indicated that proton transfer at the metal-support interface facilitates O2 binding and activation; the resulting Au-OOH species readily reacts with adsorbed Au-CO, yielding Au-COOH. Au-COOH decomposition involves proton transfer to water and was suggested to be …


Reduction Of Ketoximes To Amines By Catalytic Transfer Hydrogenation Using Raney Nickel And 2-Propanol As Hydrogen Donor, Katherynne E. Taylor May 2014

Reduction Of Ketoximes To Amines By Catalytic Transfer Hydrogenation Using Raney Nickel And 2-Propanol As Hydrogen Donor, Katherynne E. Taylor

Honors Theses

Ketoximes successfully underwent hydrogenolysis and hydrogenation under catalytic transfer conditions with Raney Nickel and 2-propanol as a hydrogen donor. Ketoximes were reduced to primary amines when 2% KOH was included in the reaction. In the absence of KOH N-isopropyl-secondary-amines were obtained in good yields.


Lanthanide-Based Precatalysts For Carbon-Carbon Bond-Forming Reactions In Aqueous Media, Derek James Averill Jan 2014

Lanthanide-Based Precatalysts For Carbon-Carbon Bond-Forming Reactions In Aqueous Media, Derek James Averill

Wayne State University Dissertations

The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln3+ ions have aroused great …


Catalytic Activity Of Heteropoly Tungstophosphoric Acid Supported On Partially Reduced Graphene Oxide Prepared By Laser And Microwave Irradiation, Mark Paul Jimena Dailo Jan 2014

Catalytic Activity Of Heteropoly Tungstophosphoric Acid Supported On Partially Reduced Graphene Oxide Prepared By Laser And Microwave Irradiation, Mark Paul Jimena Dailo

Theses and Dissertations

The solid acid catalyst of the Keggin-type 12-tungstophosphoric acid (H3PW12O40, HPW) is supported on partially reduced graphene oxide (PRGO) nanosheets for acid-catalyzed reactions. HPW is a new class of catalyst with a good thermal stability and high Bronsted acidity in order to replace common mineral acids. However, it has low specific surface area (1-5 m2/g). Therefore, the possibility of PRGO as a catalytic support for HPW is investigated due to its high surface area (2630 m2/g) and good thermal stability. The synthesis of HPW-GO catalyst is prepared using microwave and …


Electronic Effects In Oxidation Reactions Utilizing Dinuclear Copper Complexes With The Bis[3-(2-Hydroxybenzylideneamino)Phenyl] Sulfone Ligand, Armando M. Guidote Jr, Ronald L. Reyes, Riyo Kashihara, Yasuhiko Kurusu, Yoshihiro Masuyama Jan 2014

Electronic Effects In Oxidation Reactions Utilizing Dinuclear Copper Complexes With The Bis[3-(2-Hydroxybenzylideneamino)Phenyl] Sulfone Ligand, Armando M. Guidote Jr, Ronald L. Reyes, Riyo Kashihara, Yasuhiko Kurusu, Yoshihiro Masuyama

Chemistry Faculty Publications

Copper acetate and the ligands bis[3-(3-tert-butyl-2-hydroxy-5-methoxybenzylideneamino)phenyl] sulfone and bis[3-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)phenyl] sulfone were reacted to form the complexes with 2:1 copper:ligand ratio, Cu2[B(t-Bu) (OMe)BAPS](µ-OCH3)2 (4) and with 2:2 copper:ligand ratio, Cu2[B(t-Bu)2BAPS]2 (5), respectively. Structures of 4 and 5 were determined based on IR, UV-Vis, and FAB-MS data in comparison with previously characterized related copper complexes. The two complexes 4 and 5 were utilized in the oxidation of the substrates 2,4- and 2,6-di-tertbutylphenol (dtbp) at -50C with H2O2 in CH2Cl2. The coupling products are preferred in both cases. For 2,4-dtbp, yields of 4,600% and 7,200% of 3,3’,5,5’-tetra-tert-butyl-2,2’- biphenol were achieved with the use …


Alkali Promoted Molybdenum (Iv) Sulfide Based Catalysts, Development And Characterization For Alcohol Synthesis From Carbon Monoxide And Hydrogen, Belinda Delilah Molina Jan 2014

Alkali Promoted Molybdenum (Iv) Sulfide Based Catalysts, Development And Characterization For Alcohol Synthesis From Carbon Monoxide And Hydrogen, Belinda Delilah Molina

Open Access Theses & Dissertations

For more than a century transition metal sulfides (TMS) have been the anchor of hydro-processing fuels and upgrading bitumen and coal in refineries worldwide. As oil supplies dwindle and environmental laws become more stringent, there is a greater need for cleaner alternative fuels and/or synthetic fuels. The depletion of oil reserves and a rapidly increasing energy demand worldwide, together with the interest to reduce dependence on foreign oil makes alcohol production for fuels and chemicals via the Fischer Tropsch synthesis (FTS) very attractive. The original Fischer-Tropsch (FT) reaction is the heart of all gas-to-liquid technologies; it creates higher alcohols and …


Improved Synthesis, Separation, Transition Metal Coordination And Reaction Chemistry Of A New Binucleating Tetraphosphine Ligand, Ekaterina Kalachnikova Jan 2014

Improved Synthesis, Separation, Transition Metal Coordination And Reaction Chemistry Of A New Binucleating Tetraphosphine Ligand, Ekaterina Kalachnikova

LSU Doctoral Dissertations

The first chapter of this dissertation involves discussion of alkene hydration and oxidative cleavage reactions catalyzed by late transition metal complexes. Previously reported results are summarized here. Mechanistic aspects of alkene hydration catalyzed by late transition metal complexes are also explained. The second part of Chapter 1 focuses on motivation for using bimetallic nickel phosphine complexes as possible catalytic precursors for alkene hydration. Chapter 2 describes studies into alkene hydration in the presence of catalytic amounts of dinickel phosphine complexes based on linear tetraphosphine ligand, PEt2CH2CH2(Ph)PCH2P(Ph)CH2CH2PEt2, et,ph-P4. Under conditions tested no alcohol products were detected. However we have observed formation …


Preparation Of Mesoporous Silica Supported Ruthenium Oxides And The Application And Kinetic Study In The Catalysis Of Water Oxidation, Yang Zhang Oct 2013

Preparation Of Mesoporous Silica Supported Ruthenium Oxides And The Application And Kinetic Study In The Catalysis Of Water Oxidation, Yang Zhang

Open Access Dissertations

Photo-induced water splitting of water into H2 and O2 has been a major focus in the development of clean and renewable energy. The development of viable and efficient catalysts that facilitates O2 production remains the major challenge in the study of the corresponding half-reaction of water oxidation. There are plenty of metal oxides reported active in the catalysis of water oxidation. However, several important performance bench marks of those materials, such as the non-stoichiometric production of O2, slow reaction rate and/or low quantum efficiency, remain to be improved.

Ruthenium oxide (RuO2) has long been known as one of the most …


Utilization Of Biomass Derived Furans In Value-Added Organics And Heterogeneous Oxorhenium Catalysts For Deoxydehydration Of Diols, Benjamin L. Wegenhart Oct 2013

Utilization Of Biomass Derived Furans In Value-Added Organics And Heterogeneous Oxorhenium Catalysts For Deoxydehydration Of Diols, Benjamin L. Wegenhart

Open Access Dissertations

As fossil fuels are depleted, there is a growing focus on renewable chemicals based on biomass materials, including both fuels and chemical feedstocks. Current methods for biomass utilization include biological conversion to produce ethanol and various thermochemical routes (gasification, pyrolysis, liquefaction, hydrothermal treatment, etc.). Furfural is one particular chemical that can be obtained from lignocellulosic biomass in good yields through the dehydration of sugar residues. It can be used as a feedstock for chemicals such as furan and THF, or as a platform molecule for making liquid fuels. The objective of this research is to investigate new pathways for the …


Kinetic And Spectroscopic Studies Of Bicupin Oxalate Oxidase And Putative Active Site Mutants, Ellen W. Moomaw, Eric Hoffer, Patricia Moussatche, John C. Salerno Mar 2013

Kinetic And Spectroscopic Studies Of Bicupin Oxalate Oxidase And Putative Active Site Mutants, Ellen W. Moomaw, Eric Hoffer, Patricia Moussatche, John C. Salerno

Faculty Articles

Ceriporiopsis subvermispora oxalate oxidase (CsOxOx) is the first bicupin enzyme identified that catalyzes manganese-dependent oxidation of oxalate. In previous work, we have shown that the dominant contribution to catalysis comes from the monoprotonated form of oxalate binding to a form of the enzyme in which an active site carboxylic acid residue must be unprotonated. CsOxOx shares greatest sequence homology with bicupin microbial oxalate decarboxylases (OxDC) and the 241-244DASN region of the N-terminal Mn binding domain of CsOxOx is analogous to the lid region of OxDC that has been shown to determine reaction specificity. We have prepared a series of CsOxOx …


Development Of Ruthenium/Terpyridine Complexes For Water Oxidation, Dakshika Chandrashani Wanniarachchi Jan 2013

Development Of Ruthenium/Terpyridine Complexes For Water Oxidation, Dakshika Chandrashani Wanniarachchi

Wayne State University Dissertations

The work presented in the dissertation is focused on developing catalysts for water oxidation. In this regard, a series of unsysmmetrical ruthenium complexes of type [Ru(terpy-R)(phen-X)Cl]PF6 where terpy-R= 4'-(4-methylmercaptophenyl)-2,2':6'2"-terpyridine and phen-X=H (1), X= 5-nitro (2), X=5,6-dimethyl (3), and X= 3,4,7,8-tretramethyl (4) was synthesized as precursors for self-assembled monolayers. Water oxidation properties of these complexes were evaluated in the presence of (NH4)2[Ce(NO3)6] as the sacrificial oxidant by measuring catalytic turnover number (TON) after 24 h of reaction time and rate of dioxygen evolution in solution during early stages of catalysis. The results revealed that all complexes 1 - 4 are catalytic …


Toward The Advancement Of Tetraphosphine Ligand Synthesis For Homogeneous Bimetallic Catalysis, Marc Anthony Peterson Jan 2013

Toward The Advancement Of Tetraphosphine Ligand Synthesis For Homogeneous Bimetallic Catalysis, Marc Anthony Peterson

LSU Doctoral Dissertations

A tetraphosphine ligand rac-et,ph-P4 (Et2PCH2CH2(Ph)PCH2P(Ph)CH2CH2PEt2) is used for the formation of a highly active and regioselective bimetallic hydroformylation catalyst. The proposed active catalytic species in acetone, [Rh2H2(µ-CO)2(rac-et,ph- P4)]2+, is formed in situ under H2/CO pressure. This is one of the most impressive examples of cooperativity in homogeneous catalysis. The fragmentation of this catalyst by CO has been investigated and confirmed by in situ NMR spectroscopic studies. A new tetraphosphine ligand rac-et,ph-P4-Ph (et,ph-P4-Ph = Et2P(o-C6H4)P(Ph)CH2(Ph)P(o-C6H4)PEt2) has been synthesized to combat this fragmentation problem. However, the inability to successfully separate the meso and racemic diastereomers led to the attempted alteration of the …


New Bimetallic Iridium Cluster Carbonyl Complexes, Mingwei Chen Jan 2013

New Bimetallic Iridium Cluster Carbonyl Complexes, Mingwei Chen

Theses and Dissertations

Platinum group metal derived bimetallic clusters have been used as precursors to nanoscale catalysts which have been proven to be more effective than their monometallic counterparts. Iridium is a platinum group metal and its applications in catalysis continue to grow. To take advantages of synergies between mixed-metals, we modified iridium clusters with other metal ligands like tin, germanium, and group IB (gold, silver, copper) etc. and obtained a fairly large amount of new iridium derived bimetallic clusters which could be precursors to catalysts with superior properties than that available nowadays. The reaction of Ir4(CO)12 with Ph3SnOH in the presence of …


Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee Jan 2013

Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee

Applied Research Center Publications

Brust–Schiffrin reduction of Pd and Pt precursors in the presence of resorcinarene amine surfactant led to the formation of substantially Pt rich, PdPt bimetallic nanoparticles of a V-shape or variants on the V-shape. New insights into this reaction are provided on the basis of reversed Brust–Schiffrin syntheses, DLS, UV-vis, and NMR analysis. Based on our experiments we conclude that the resorcinarene amine surfactant is part of the inverse micelle formed from TOABr and it also selectively complexes with the Pd salts prior to their reduction. Remarkably, the composition of the bipodal nanoparticles could be varied substantially by varying the reaction …


Investigations Into Alkene Hydration And Alkene Oxidation Catalysis, William Schreiter Jan 2013

Investigations Into Alkene Hydration And Alkene Oxidation Catalysis, William Schreiter

LSU Doctoral Dissertations

Bimetallic Ni complexes Ni21M and Ni21R and monometallic transition metal complexes were investigated as possible alkene hydration catalysts under a multitude of different reaction conditions. All attempts at performing this catalytic reaction failed to give any alcohol products. Catalytic screening experiments were conducted using a mixture of racemic-et,ph-P4 and meso-et,ph-P4, 1M and 1R, and various transition metals. These experiments gave several different products including 1-phenylethanol from styrene. During the course of the hydration experiments, an aldehyde product was identified from experiments conducted with the bimetallic complexes in air. Experiments have shown that the aldehyde is produced from the oxidative cleavage …


Asymmetric Nitrene Transfer Reactions With Azides Via Co(Ii)-Based Metalloradical Catalysis (Mrc), Jingran Tao Jan 2013

Asymmetric Nitrene Transfer Reactions With Azides Via Co(Ii)-Based Metalloradical Catalysis (Mrc), Jingran Tao

USF Tampa Graduate Theses and Dissertations

Asymmetric nitrene transfer reactions via metalloradical catalysis (MRC) with

azides has attracted research interest because of its fundamental and practical importance.

The resulting nitrogen-containing units are recurrent motifs in biologically important

molecules and can serve as versatile precursors in organic synthesis.

The [Co(D2-Por*)] have emerged as a new class of catalysts for asymmetric

aziridination and C-H amination. These metalloradical catalysts have been shown to be

highly effective for the asymmetric intermolecular aziridination of a broad scope of

substrates with different classes of azides with excellent to good enantioselectivity. The

intramolecular C-H amination utilizing various azides can allow for the construction …


Model Pt- And Pd-Based Electrocatalysts For Low Temperature Fuel Cells Applications, Selasi Ofoe Blavo Jan 2013

Model Pt- And Pd-Based Electrocatalysts For Low Temperature Fuel Cells Applications, Selasi Ofoe Blavo

USF Tampa Graduate Theses and Dissertations

In the search for alternative energy technologies, low temperature fuel cells continue to feature as technologies with the most promise for mass commercialization. Among the low temperature fuel cells, alkaline and proton exchange membrane fuel cells are the most popular. Alkaline fuel cells have typically been used for water generation as well as auxiliary power for space shuttles. Their bulkiness however makes them undesirable for other applications, especially in automobiles, where there is a great demand for alternative technologies to internal combustion engines. Proton exchange membrane fuel cells on the other hand possess numerous qualities including their compact size, high …


Capturing Fleeting Intermediates In A Catalytic C-H Amination Reaction Cycle, Richard H. Perry, Thomas J. Cahill Iii, Jennifer L. Roizen, Justin Du Bois, Richard N. Zare Nov 2012

Capturing Fleeting Intermediates In A Catalytic C-H Amination Reaction Cycle, Richard H. Perry, Thomas J. Cahill Iii, Jennifer L. Roizen, Justin Du Bois, Richard N. Zare

Chemistry and Physics Faculty Articles

We have applied an ambient ionization technique, desorption electrospray ionization MS, to identify transient reactive species of an archetypal C–H amination reaction catalyzed by a dirhodium tetracarboxylate complex. Using this analytical method, we have detected previously proposed short-lived reaction intermediates, including two nitrenoid complexes that differ in oxidation state. Our findings suggest that an Rh-nitrene oxidant can react with hydrocarbon substrates through a hydrogen atom abstraction pathway and raise the intriguing possibility that two catalytic C–H amination pathways may be operative in a typical bulk solution reaction. As highlighted by these results, desorption electrospray ionization MS should have broad applicability …


Polystyrenesulfonate-Catalyzed Synthesis Of Novel Pyrroles Through Paal-Knorr Reaction, Mandira Banik, Bianca Ramirez, Ashwini Reddy, Debasish Bandyopadhyay, Bimal K. Banik Mar 2012

Polystyrenesulfonate-Catalyzed Synthesis Of Novel Pyrroles Through Paal-Knorr Reaction, Mandira Banik, Bianca Ramirez, Ashwini Reddy, Debasish Bandyopadhyay, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Background: The classical Paal-Knorr reaction is one of the simplest and most economical methods for the synthesis of biologically important and pharmacologically useful pyrrole derivatives.

Results: Polystyrenesulfonate-catalyzed simple synthesis of substituted pyrroles following Paal-Knorr reaction has been accomplished with an excellent yield in aqueous solution. This method also produces pyrroles with multicyclic polyaromatic amines.

Conclusions: The present procedure for the synthesis of N-polyaromatic substituted pyrroles will find application in the synthesis of potent biologically active molecules.


A Microwave-Assisted Bismuth Nitrate-Catalyzed Unique Route Toward 1,4-Dihydropyridines, Debasish Bandyopadhyay, Stephanie Maldonado, Bimal K. Banik Mar 2012

A Microwave-Assisted Bismuth Nitrate-Catalyzed Unique Route Toward 1,4-Dihydropyridines, Debasish Bandyopadhyay, Stephanie Maldonado, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The classical Hantzsch reaction is one of the simplest and most economical methods for the synthesis of biologically important and pharmacologically useful 1,4-dihydropyridine derivatives. Bismuth nitrate pentahydrate under microwave irradiation is proven to act as a very efficient catalyst for a one-pot, three-component synthesis of 1,4-dihydropyridines in excellent yields from diverse amines/ammonium acetate, aldehydes and 1,3-dicarbonyl compounds within 1-3 min under solvent-free conditions. The present environmentally benign procedure for the synthesis of 1,4-dihydropyridines is suitable for library synthesis and it will find application in the synthesis of potent biologically active molecules. The excellent yield and extreme rapidity of the method …


Synthesis, Structural Characterization, And Benzyl Alcohol Oxidation Activity Of Mononuclear Manganese(Ii) Complex With 2,2'-Bipyridine: [Mn(Bipy)_2(Clo_4)_2], İbrahi̇m Kani̇, Mehmet Kurtça Jan 2012

Synthesis, Structural Characterization, And Benzyl Alcohol Oxidation Activity Of Mononuclear Manganese(Ii) Complex With 2,2'-Bipyridine: [Mn(Bipy)_2(Clo_4)_2], İbrahi̇m Kani̇, Mehmet Kurtça

Turkish Journal of Chemistry

A manganese(II) complex of 2,2'-bipyridine (bipy) was synthesized and characterized by X-ray diffraction, IR, and UV-vis spectroscopy. The activity of the complex was tested for oxidation of benzyl alcohols using t-BuOOH as an oxidant in organic solvents and in an organic/water biphasic system (hexane/H_2O, toluene/H_2O). The effect of solvent, temperature, oxidant, and some additives (KBr, N(C_4H_9)Br, and N-bromosuccinimide) on the oxidation of benzyl alcohol is reported. The results show that benzyl alcohol was selectively converted to benzaldehyde in 71.9% yield within 4 h in acetonitrile. Control experiments performed without catalyst and the corresponding metal salt as catalyst produced no benzaldehyde …


Studies Of A Dirhodium Tetraphosphine Catalyst For Hydroformylation And Aldehyde-Water Shift Catalysis, Aaron Rider Barnum Jan 2012

Studies Of A Dirhodium Tetraphosphine Catalyst For Hydroformylation And Aldehyde-Water Shift Catalysis, Aaron Rider Barnum

LSU Doctoral Dissertations

Research into the dirhodium tetraphosphine catalyst precursor [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 shows it is capable of forming a highly active and regioselective hydroformylation catalyst in situ when using an acetone or acetone/water solvent. Hydroformylation experiments (using 1-hexene), FT-IR studies, and acid-base studies were performed to better understand the various complexes of the dirhodium catalyst cycle. These studies lead to the newly proposed catalyst mechanism when performed in an acetone/water solution, using the monocationic [rac-Rh2(H)(µ-CO)2(CO) (et,ph-P4)]+ as the proposed active catalyst complex for hydroformylation. For the conversion of 1-hexene to heptanal, it is capable of performing an initial rate of 30 turnovers per min, …


Asymmetric Intra- And Intermolecular Cyclopropanation By Co(Ii)- Based Metalloradical Catalysis, Xue Xu Jan 2012

Asymmetric Intra- And Intermolecular Cyclopropanation By Co(Ii)- Based Metalloradical Catalysis, Xue Xu

USF Tampa Graduate Theses and Dissertations

Metal-catalyzed cyclopropanation of olefins with diazo reagents has attracted research interest because of its fundamental and practical importance. The resulting cyclopropyl units are recurrent motifs in biologically important molecules and can serve as versatile precursors in organic synthesis. Since they were first introduced in 2004, Co(II) complexes of D2-symmetric chiral amidoporphyrins [Co(D2-Por*)] have emerged as a new class of catalysts for asymmetric cyclopropanation. These metalloradical catalysts have been shown to be highly effective for asymmetric intermolecular cyclopropanation of a broad scope of substrates with different classes of carbene sources, particularly including electron-deficient olefins and acceptor/acceptor-substituted …


Direct Contact Pyrolysis Of Hydrocarbons: A Source Of Hydrogen And Interesting Carbon Formations, Peter G. Faught Dec 2011

Direct Contact Pyrolysis Of Hydrocarbons: A Source Of Hydrogen And Interesting Carbon Formations, Peter G. Faught

UNLV Theses, Dissertations, Professional Papers, and Capstones

The work detailed in this document looks at a novel liquid metal supported catalytic system for the generation of hydrogen by decomposition of ethanol through direct contact pyrolysis. The hydrogen is produced at relatively low temperatures (500-600°C) and has carbon and water as co-products. It should be noted that CO is not observed as a product at these low temperatures. This is to be contrasted with the hydrogen produced at higher temperature from ethanol which does contain carbon monoxide. The presence of carbon monoxide in hydrogen complicates fuel cell operation and catalytic chemical processes. Thus, the lack of CO in …


Preparation And Characterization Of A Composite Of Gold Nanoparticles And Single-Walled Carbon Nanotubes And Its Potential For Heterogeneous Catalysis, Anne Shanahan, James Sullivan, Mary Mcnamara, Hugh Byrne Oct 2011

Preparation And Characterization Of A Composite Of Gold Nanoparticles And Single-Walled Carbon Nanotubes And Its Potential For Heterogeneous Catalysis, Anne Shanahan, James Sullivan, Mary Mcnamara, Hugh Byrne

Articles

A single-walled carbon nanotube-supported gold nanoparticle composite was prepared and characterized by X-ray diffraction, scanning transmission electron microscopy/scanning electron microscopy/transmission electron microscopy, energy-dispersive X-ray analysis, atomic absorption spectroscopy, nitrogen adsorption, Raman spectroscopy, and ultraviolet-visible spectroscopy. The Au particles were found to be crystalline, with a well-defined and narrow particle-size distribution, centered around 7 nm. The activity and selectivity of the composite for solventless aerobic oxidation of a secondary alcohol were examined, and a conversion efficiency of 95% was obtained.


Synthetic And Mechanistic Studies Of Coupling Reactions Involving C-H Bond Activation, Ki Hyeok Kwon Jul 2011

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 …