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bagherzadeh--mojtaba
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Synthesis, Structure and Catalytic Application of Mn, Fe and Mo Complexes with Schiff base and Oxazoline ligands and Theoretical Mechanistic Studies on the Role of Heme and non-Heme Iron(IV)-Oxo Species in Hydroxylation and Epoxidation Reactions
, Ph.D. Dissertation Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
The first part of this thesis describes the synthesis and characterization of several Mn, Fe and Mo complexes containing tridentate Schiff base and oxazoline ligands and their reactivities as catalysts in the oxidation of organic compounds like olefins and sulfides, as well. The crystal structures of newly prepared cis-dioxo-bis[2-(2′-hydroxyphenyl)-oxazolinato]molybdenum(VI), cis-[MoO2(phox)2] and (N-hydroxyphenyl-salicylidenamine)(acetylacetonato)ethanol iron(III), [FeIII(N-OPh-sal)(acac)EtOH] complexes have been described by X-ray crystallography. Due to the difficulties in the preparation of suitable single crystals of novel...
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
Inert gold become catalytically active when dispersed in the form of nanoparticles. Isolated gold nanoparticles have demonstrated high catalytic activity for both oxidation and reduction reactions. In order to obtain high catalytic activity, gold nanoparticles are generally dispersed on support materials, among which oxides are commonly used. However, a substantial decrease in activity and selectivity of the immobilized catalysts is frequently observed due to the heterogeneous nature of these support materials in reaction media. In the course of our study on the metal-based catalysis for synthesis of organic compounds, we herein report that rod-shaped Au nanoparticles in aqua solution...
Synthesis and Characterization of a novel Ruthenium(II) Complex With Bidentate O,N-donor OxazolineLigand and Study of Catalytic Oxidation of Sulfides and Alkanes
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
The 2-(2′-hydroxyphenyl)-oxazoline ligand (Hphox) is generated from 1:1 condensation of methyl salicylate with 2-aminoethanol. Novel [Ru(Hphox)2(H2O)2] (Hphox = 2-(2′-hydroxyphenyl)-oxazoline ) complex has been synthesized and characterized by physic-chemical methods. Oxidation of sulfides catalyzed by the mixed-ligand ruthenium(II) complex [Ru(Hphox)2(H2O)2]using urea-hydrogen peroxide (UHP) as oxidant was investigated under mild condition within 1 h. The results showed that mixed-ligand ruthenium(II) complex was effective catalyst in oxidation of sulfides in whichsulfoxideswere the only products. Using this catalytic system in the oxidation of alkanes, ketones were obtained as the main...
Synthesis of Core-Shell Nanoparticles Supported Iron and Vanadium Schiff Base and Their Application as a Catalyst for Oxidation of Sulfides, Alcohols and Olefins
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In this work, synthesized Fe3O4 magnetic nanoparticles andcoated with SiO2 to prepare magnetic core-shell nanoparticles. Then immobilized Schiff baseof iron and vanadium complexes on magnetic core-shell nanoparticles was prepared as a recoverable magnetic nano catalysts. These catalysts were named Fe3O4@SiO2@L1@Fe, Fe3O4@SiO2@L2@Fe and Fe3O4@SiO2@L3@V. Furthermore,olefines epoxidation, sulfides and alcohols oxidation were studied with using iron and vanadium magnetic nano catalysts. The supported catalysts were characterized by atomic absorption, FT-IR and UV–Vis spectra.The catalytic performance of the synthesized iron catalyst was tested for the epoxidation of cyclohexene, styrene and...
Preparation of Heterogeneous Catalysts by Immobilization of Molybdenum and Manganese-shiff Base Complexes into the Nanopores of Zeolite and SBA-15
, Ph.D. Dissertation Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
This thesisconsiders new fundamental approaches to yield heterogeneous catalysts in to three sections. The first section described the immobilization of the molybdenum-Schiff base complexes in pores of SBA-15 in two different methodologies depending on the actual structure of the complexes., (i) stepwise formation of the complex by initial covalent anchoring of one of the components and consecutive solid phase synthesis consisting of the condensation of the other components of the salen complex (iii) one-step complex immobilization by covalent binding through the ligand.Based on the first methodology, we report the preparation of ordered mesoporous silica SBA-15 containing a molybdenum...
Synthesis and Characterization of Various Transition Metal Complexes and the Application in Oxidation, Heck, Suzuki, Sonogashira and Olefin Metathesis
, Ph.D. Dissertation Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In nature, catalysis is of vital importance in a wide variety of biochemical processes catalyzed by metalloenzymes. The functions performed by the metalloenzymes and their significance have inspired a range of biomimetic studies, and intense efforts have been concentrated on the synthesis of low molecular weight complexes to model the spectroscopic features of such enzymes. Concomitantly, a challenging frontier in the field of biomimetic chemistry is the development of highly reactive model compounds that are able to effect rapid and selective substrate conversion. Some important catalytic transformations that have gained attention in recent years involve the carbon-carbon coupling, olefin...
Synthesis and Study of Catalytic Reactivity Oxo Vanadium (IV)& (V) Complexes with N,N'-Ethylenebis(Salicylimine)Ligand in Oxidation of Sulfides and Epioxidation of Olfins by Urea Hydrogen Peroxide (UHP) and Tert-Butyl Hydroperoxide (TBHP)
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
The selective oxidation of sulfides to sulfoxides is an important method in organic synthesis because sulfoxides are useful synthetic intermediates for the construction of various chemically and biologically significant molecules. To date, the most important method of preparation involves the oxidation of sulfides. Various oxidizing agents are used for this purpose. Oxovanadium(IV)(Salen) and oxovanadium(V)(Salen)Cl were synthesised and screened in the vanadium-catalysed oxidation of sulfides to solfuxides with urea hydrogen peroxide(UHP) as terminal oxidant. Both complexes showed good activity and selectivity trough the catalytic reaction.characterized by elemental analyses, IR, 1H and 13C...
Synthesis and Characterization of Cis-dioxomolybdenum(VI) Complex with an ONOtype Tridentate Schiff base Ligand and its Application as a Catalyst for Epoxidation of Olefinsin Water
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
New dioxomolybdenum(VI) complex has been synthesized by reacting N-hydroxyphenyl-[5-(triphenylphosphonium)methyl]salicylideneamine chloride (PPh3-H2sap) as a water soluble ligand and [MoO2(acac)2] in ethanolic solution. The water soluble ligand (PPh3-H2sap) was prepared by reaction of 2-aminophenol with (3-formyl-4-hydroxybenzyl)triphenylphosphonium chloride as a water solublesalicylaldehyde derivative. The resulting complex with the formula [MoO2(PPh3-H2sap)(EtOH)] which contains an ethanol molecule in sixth site of coordination, was characterized by elemental analyses, 1H NMR,31P NMR, IR and UV-Vis spectroscopic studies. This complex was tested as a catalyst for the homogeneous...
Synthesis and Characterization of Bis[2-(2׳-Hydroxyphenyl)- -oxazolinato]Ni(II) Complex and Investigation of it׳s Catalytic Activity in C-C Coupling Heck Reaction
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In this study a new Ni(II)-¬oxazoline complex was synthesized by reaction of Ni(CH3COO)2.4H2O and 2-(2׳-hydroxyphenyl)-2-oxazoline ligand in MeOH solvent. The resulting complex bis[2-(2׳-hydroxyphenyl)-2-oxazolinato]Ni(II), was characterized by different spectroscopic methods. X-ray diffraction showed that this complex is four coordinated with a square planner geometry. The complex was applied as an efficient homogeneous catalyst in C-C coupling Heck reaction of arylhalides with olefins such as methylacrylate. Investigation of the catalytic activity of the complex in Heck reaction between arylhalides and olefins showed high yield and selectivity. For example reaction between iodobenzene and...
Heterogenization of Ionic Complexes of Mo(VI) with Sulfonated Schiff Base Ligands on the Polysiloxane as Support for Catalytic Epoxidation of Olefins
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In this project a new molybdenum (VI) complex with tetradentate Schiff base ligand which was soluble in water was synthesized and characterized. In the first step of ligand synthesis, the reaction was performed between salicylaldehyde and aniline, and then used concentrated sulfuric acid for sulfonation. In the next step 5- sulfosalicylaldehyde sodium salt was formed by removing of aniline with heating and using sodium carbonate. In the presence of ethylendiamine and bis (acetylacetonato) dioxomolybdenum(VI) the final product, cis-dioxo sodium (N,N-bis (5-sulfonatosalicyldene)1,2-diaminoethane) molybdenum (VI) complex was synthesized. The complex was characterized by (CHN) elemental...
Synthesis of Metal-Organic Frameworks and Self-supported Coordination Polymers of Transition Metals with Catalytic Potential as Template for Supported Pd Nanoparticles and Preparation of Metal Oxide Nanoparticles for Olefin Epoxidation and C-C Coupling Reactions
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In this research, synthesis of new heterogeneous catalysts has been studied. These catalysts were prepared in three different areas of the synthesis of coordination polymers and metal-organic frameworks, supported palladium nanoparticles on these polymers, and production of metal oxide nanoparticles. At first, metal organic frameworks of cobalt and manganese transition metals were synthesized through hydrothermal method. In order to prepare these frameworks, 1,4-benzenedicarboxylic acid (terephthalic acid) and 2-amino-1,4-benzenedicarboxylic acid ligands were utilized as spacer ligands. X-ray analysis indicated that the structure of polymers is composed of secondary building units (SBUs) of...
Synthesis and Characterization of Cis-dioxomolybdenum(VI) Complex with an ONO Type Tridentate Schiff base Ligand and its Application as Catalyst for Epoxidation of Olefins
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
A new dioxomolybdenum(VI) complex, (Cis-[MoO2(L)])n, has been synthesized by reacting 4-bromo-2-((2-hydroxy-5-methylphenylimino)methyl)phenol as a ligand and [MoO2(acac)2] in methanolic solution. For characterization and structure determination of the synthesized complex, different techniques were performed such as elemental analyses, 1H NMR, IR, UV-Vis and X-ray crystallography. The complex was tested as a catalyst for the homogeneous epoxidation of olefins, using tert-butyl hydperoxide (TBHP) as an oxidant. The catalytic system showed high yield, selectivity and turnover number in olefin epoxidation reactions under atmospheric conditions. For example, when the molar ratio of catalyst,...
Synthesis and Study of Catalytic Activity of Iron (III)-bis(2-oxazolinyl) Methane complex by Urea Hydrogen Peroxide in Oxidation of Sulfides
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
Considerable effort has been directed in recent years towards the transition metal complex catalyzed oxidation of organic compounds. Herein the synthsis of the iron complex of bis(oxazoline) ligand as a novel catalyst is reported, and the catalytic activity of this complex in oxidation of sulfides is investigated. Bis(2-oxazolynil)methane as ligand is prepared by condensation of diethylmalonate with 2-aminoethanole in 1:2 molar ratio and finally corresponding complex is synthesized by the reaction between FeCl3.6H2O and Bis(2-Oxazolynil)methane in 1:1 molar ratio. The complex is characterized by using IR, UV-Vis, cyclic voltametery, conductometery and elemental analysis data. Moreover,...
Synthesis and Characterization of Cu(II) Complexes with an Bidentate N,O-type Schiff Base Ligands and Study of the Catalytic Properties in Click Reactions
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
Two new copper(II) complexes, [CuL2] and [Cu(phox)2], were synthesized by reaction of 1-((4-bromophenylimino)methyl)naphthalen-2-ol, HL, and 2-(2′-hydroxyphenyl)-2-oxazoline, Hphox, as ligands and copper(II) acetate mono-hydrate with the ratio 2:1 (ligand:metal), respectively. For characterization and structure determination of synthesized complexes, different techniques were performed such as FT-IR, elemental analyses (CHN), and X-ray crystallography. The geometry around Cu atom is almost square planar in both complexes. The catalytic activity of the complexes was evaluated in azide–alkyne cycloaddition reaction in water without need of any additional agent. The reaction conditions for the...
Immobilazation of Manganese-Porphyrin Complex on Magnetic Nanoparticles and its Application as a Catalyst for the Epoxidation of Olefins and Oxidation of Sulfides
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
The goal of this study is to synthesise and study the catalytic properties of a Mn-Porphyrin complex fixed on a magnetic nanoparticle bed. This nanocatalyst was used in oxidation of sulfides and epoxylation of olefin. In the multistage synthesis of this catalyst, iron oxide magnetic nanoparticles were first prepared, then, by silanizing these nanoparticles, and then using the 3-chloropropyltrimethoxy methanol reactor, Immobilzation the material on the substrate and immediately react in reaction Substitution of the nucleus of friendship and using a sodium azide reaction, bromide is replaced by azide. Subsequently, by synthesising 4-hydroxy porphyrin and replacing one of its positions with...
Green Synthesis, Characterization and Application of the Nanomaterials Based on Aluminum Fumarate Metal-Organic Frameworks for Targeted and Smart Delivery and Release of Doxorubicin
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In this research, an attempt was made to increase the efficiency and effectiveness of the targeted and controlled release systems of the anticancer drug (doxorubicin) by using inorganic and organic compounds as well as inorganic-organic hybrids. For this purpose, a whole class of aluminum fumarate metal-organic frameworks-based and reduced-graphene oxide nanocarriers were synthesized and using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectroscopy (XRD), scanning electron microscope (FESEM) and atomic force microscope (AFM) analysis were characterized, and their nano-composites based on organotin-complexes with the approach of achieving a stable drug delivery system,...
Synthesis and Characterization of Transition Metal Complexes Supported on Carbon-Based Nanocomposites and Their Application as Gene and Drug Delivery Systems
, Ph.D. Dissertation Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In this dissertation, an attempt has been made to optimize some smart nanocarriers and the controllable release of drug (doxorubicin) and genetic material (plasmid CRISPR). Regarding, some metal nanoparticles, metal-organic frameworks, transition metal complexes, graphene oxide, and functionalized carbon nanotubes have been synthesized and also characterized and their hybrids and nanocomposites have been prepared successfully. All the abovementioned nanomaterials were designed and synthesized due to achieve biodegradable, biocompatible, higher positive surface potential, lower cytotoxicity, better responsivity to stimulus, and greener compounds. Doxorubicin and plasmid CRISPR has been...
Preparation of Thin-Film Nanocomposite Membranes Based on Metal-Organic Frameworks (Mofs) and Study of their Performance in Forward Osmosis (Fo) Process
, Ph.D. Dissertation Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
The forward osmosis (FO) process is a high potential emerging membrane process in the seawater desalination and contaminated water treatment fields. One of the main challenges facing this process is the weak separation (high reverse solute flux, low water flux, and insufficient selectivity) and antifouling performances of its membranes. Various sections of this study focus on the development of FO membranes and their performance improvement. For this purpose, thin-film composite membranes with the same combination of polyethersulfone/polyamide (PES/PA) have been used to investigate the effect of metal-organic frameworks (MOFs) introduction on their performance. The support layer in all cases...
Preparation of Magnetically Recyclable Silica Supported Oxovanadium Nanocatalyst and its Application in the Oxidation of Sulfides
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
Current study reports a state-of-the-art approach for synthesis of nanocatalyst based on Oxo-vanadium Schiff base complex which itself is, covalently, immobilized on core-shell magnetic nanoparticles of silica-modified magnetite (Fe3O4@SiO2) and the substantial potential it offers as heterogeneous catalyst in selective oxidation of sulfides.Synthesized materials and complexes in this project were characterized by means of modern spectral devices such as FT-IR, XRD and SEM.Unlike routine process of the preparation of heterogeneous catalysts that requires further modification of the core-shell nanoparticles with capping agents, here we have been capable of cutting some time-consuming steps...
Study of Catalytic Activity of Zirconium-Based Metal-Organic Frameworks in the Epoxide Ring-Opening Reactions
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor)
Abstract
In current research, two zirconium-based metal-organic frameworks, MIP-202 (Zr) and UIO-66(CO2H)2 were employed as catalysts in the epoxy ring-opening reactions by amino and alcoholic nucleophiles. Firstly, these metal-organic frameworks were prepared under mild synthetic conditions and then characterized by means of spectral techniques such as X-ray diffraction (XRD), nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR), electron microscopy Scanning (SEM) and X-ray energy diffraction (EDAX) spectroscopy were confirmed. Finally, their catalytic activity in epoxy ring-opening reactions was investigated and in to determine optimal conditions, the...