Sharif Digital Repository

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,... 

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... 

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... 

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... 

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... 

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... 

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... 

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... 

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... 

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... 

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... 

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... 

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,... 

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... 

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... 

The main aim of present thesis is to synthesis and characterize of ferrite nanocomposites as a new generation phtocalyst and their application in degradation of various types of environmental pollutants in different irradiation time and dark conditions. Ferrites have been used anchored to carbon allotropes such as graphene oxide and carbon nanotubes, in order to improve their photocalytic activity as well as phase structure, textural and optical properties. Firstly, a new SnS2-BiFeO3/rGO nanocomposite has been prepared to increase the visible-light-responsive photodegradation of organic dyes such as cationic methylene blue (MB) and anionic methyl orange (MO). The obtained results showed... 

In this study, a polyoxotungestate containing copper was impregnated as catalyst on a magnetic metal-organic framework (Fe3O4/MIL-101(Cr)). Initially, the desired polyoxotungestate was synthesized using sodium tungestate and sodium metasilicate salts and then copper(ІІ) ion was fixed on it. Subsequently, the MIL-101(Cr) metal-organic framework was prepared by solvothermal method; using chromium nitrate salt and 1,4-benzen dicarboxylic acid at 220 ◦C and was magnetized by co-precipitation method. Finally, the corresponding polyoxotungestate was stirred at ambient temperature for 24 h with MIL-101(Cr) and then the brown precipitate was separated using a magnet. Different techniques such as IR,... 

In this work heterogenization of manganese porphyrins in ZIF-8 and Mg-Al-LDHs structures is performed, via host-guest interactions, and their catalytic activities for olefins epoxidation are also investigated.A heterogenized meso-tetrakis(2,3-dihydroxyphenyl)porphyrinatomanganese(III) acetate at zeolite imidazolate framework-8 (T(2,3-OHP)PorMn@ZIF-8) is investigated in the catalytic olefin epoxidation reactions at room temperature at the first part. Heterogenization is done through a non-classical hydrogen bond proposed between T(2,3-OHP)PorMn bearing O-H groups and C-H of the 2-methylimidazolate linkers in ZIF-8 structure. The aforementioned compound characterized by X-ray powder... 

In this study, two layer nanocomposite membrane of polyethersulfone (support layer) and polyamide (active layer) were prepared for the purpose of desalination of water by forward osmosis method. In order to take more advantage of this membrane, montmorillonite nanoparticles which had been modified by graphene oxide were placed in it. To bind the nanoparticle components together, at first, montmorillonite was functionalized by (3-Aminopropyl) triethoxysilane to increase its nucleophilicity, and for graphene oxide to increase its electrophilicity, thionyl chloride was added. The two compounds were mixed and stirred for 24 hours in the presence of triethylamine base by magnetic stirrer at 30°C... 

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...