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    Molybdenum(VI) Complexes and Palladium Nanoparticles in Ionic Liquid-Liquid Biphasic and Supported Ionic Liquid phase (SILP) Catalysis, and Green Catalytic Processes using Polymeric Ionic Liquids (PILs

    , Ph.D. Dissertation Sharif University of Technology Ghazali-Esfahani, Saeideh (Author) ; Bagherzadeh, Mojtaba (Supervisor)
    Abstract
    In this thesis, ionic liquids and polymeric ionic liquids were investigated as solvent and support for immobilization of molybdenum and palladium catalysts. Three newly synthesized room temperature ionic liquids containing molybdate anion, [DMIm][MoO2(NCS)4], [RPy][MoO2(NCS)4] (R = butyl or decyl), and previously reported [BMIm][MoO2(NCS)4] were used as catalysts for the reduction of sulfoxides. For facilitating the recyclability of the catalysts, the ionic liquid solvents, [RMIm][PF6] and [RPy][PF6] (RMIm=1-n-alkyl-3-methylimidazolium, RPy= 1-n-alkylpyridinium), were applied to immobilize molybdenum catalysts. These catalysts showed high catalytic activity for sulfoxide reduction in this... 

    Synthesis of Pincer Palladium Complexes and Molybdenium, Gold and Platinum Complexes Containing Azulene Based Ligands: Catalytic and Optical Properties Studies

    , Ph.D. Dissertation Sharif University of Technology Mousavi, Nargesalsadat (Author) ; Bagherzadeh, Mojtaba (Supervisor) ; Jamali, Sirous (Supervisor)
    Abstract
    There are two parts in this thesis. The first one is about the synthesis of azulene based compounds, which are characterized by 13C and 1H NMR. These compounds were included in three imine ligands (1,2 and 3) and a NHC ligand (4). Azulene based materials shows a fluorescence emission. The stimuli-responsive emissive azulene derivatives are very rare. herein, we report the synthesis of stimuli responsive emissive 1- and 1,3-disubstitution azulene-based compounds that can switch on and off the emission upon protonation with trifluoroacetic acid (TFAH) and deprotonation with triethylamine respectively. The type of transitions were studied by computational calculations. The complexation of some... 

    Synthesis and Characterization of Tungsten (VI)Complex with Oxazine Ligand and its Catalytic Application in Oxidation of Sulfides to Sulfoxides

    , M.Sc. Thesis Sharif University of Technology Esmailpour Firoozsalary, Parvin (Author) ; Bagherzadeh, Mojtaba (Supervisor)
    Abstract
    In this study a novel oxo-diperoxo tungsten(VI) complex [WO(O2)2(phox)] was prepared by reaction of WO3 in H2O2 with oxazine-type ligand, 2-(2′-hydroxyphenyl)-5,6-dihydro-1,3-oxazine (Hphox). The complex was characterized by FTIR, 1H NMR and elemental analysis. The single-crystal X-ray diffraction studies revealed a seven coordinate tungsten center with a distorted octahedral geometry. The [WO(O2)2(phox)] complex was applied as a catalyst in efficient, and selective oxidation of sulfide to sulfoxide using 30% H2O2 or UHP as oxidants. This catalyst showed excellent catalytic activities and high selectivities in producing a variety of aryl and alkyl sulfoxides under mild conditions. To get... 

    Synthesis of Novel Bimetallic Nanocomposite of Copper and Silver Based on Metal Organic Frameworks and Investigation of Its Application as Catalyst in Sulfonation Reaction

    , M.Sc. Thesis Sharif University of Technology Yaghoubnejad Pazoki, Parisa (Author) ; Matloubi Moghaddam, Firouz (Supervisor)
    Abstract
    In recent years, bimetallic metal-organic frameworks have attracted the great attention of researchers due to their dual properties and synergistic effects. In this research and inspired by green chemistry, the synthesis of a magnetic nanocomposite of the defective green metal-organic framework was implemented, which carries metallic silver nanoparticles (Ag NPs@Cu-MOF). Then, the sulfonated compounds were synthesized with the prepared nanocomposite because of the importance and widespread medicinal use of sulfur-containing compounds especially sulfonated compounds, and the difficulty of their preparation methods. It is noteworthy to mention that the sulfonation reaction was done by... 

    Synthesis of Magnetically Recyclable Core-shell Nanocatalysts for Epoxidation of Alkenes and Reduction of Sulfoxide to Sulfides and Oxygen Atom transfer by Mo(VI) Complexes

    , Ph.D. Dissertation Sharif University of Technology Haghdoost Manjili, Mohammad Mehdi (Author) ; Bagherzadeh, Mojtaba (Supervisor)
    Abstract
    In the first part of this thesis, the application of core-shell magnetic nanoparticles supported V(V), Mo(VI) and Mn(III) complexes in the catalytic oxidation and reduction reactions was discussed. A magnetically recyclable vanadium(V) catalyst was synthesized by covalent anchoring of VO(salen)Cl on silica coated Fe3O4 nanoparticles. These nanoparticles were efficient catalysts for selective oxidation of sulfides to corresponding sulfoxides with urea hydrogen peroxide in excellent yields. Leaching and recycling experiments revealed that the nanocatalyst can be applied for nearly complete oxidation of sulfides for at least five successive cycles. A manganese(III) complex was immobilized on... 

    The stereoselective synthesis of the tetrahydrothiopyranolr ,Y'-blindole skeletons via tandem reaction of indoline- r-thiones to Baylis-Hillman adduct acetates & Silica-Supported DABCO-tribromide: A New, Versatile and Recyclable Catalyst for the Chemoselective Oxidation of Sulfides to Sulfoxides and Oxidative Coupling of Thiols into Disulfides

    , M.Sc. Thesis Sharif University of Technology Sobhani, Maryam (Author) ; Matloubi Moghaddam, Firouz (Supervisor)
    Abstract
    We have reported a new and efficient synthesis of tetrahydrothiopyrano [2,3-b]indole skeletons via unique tandem reaction of indoline-2-thiones to Baylis-Hillman adduct acetates. This protocol is a very mild and simple method for construction heterocycles in a one-step process. This is a convenient and diastereoselective synthesis of methyl 4-aryl-2,3,4,9-tetrahydrothiopyrano[2,3-b]indole-3-carboxylate systems in the presence of K2CO3 in acetonitrile. The major benefits of the current study are the one-pot procedure, high yields and diastereoselectivity, short reaction times and the similarity of the products to the biologically active moieties.
    In addition 1, 4-diazabicyclo [2.2.2]... 

    Synthesis, Characterization and Catalytic Activity of Vanadium(v) Complex with Tridentate Schiff Base Ligand N´-[1-(2-Hydroxynaphthyl) Methylene]-2-Hydroxy Benzohydrazide

    , M.Sc. Thesis Sharif University of Technology Mahmood Khanlu, Reza (Author) ; Bagherzadeh, Mojtaba (Supervisor) ; Mohammadi Boghaei, Davar (Supervisor)
    Abstract
    In this project a new dioxovanadium (V) complex of Schiff base ligand N`-[1-(2-hydroxynaphthyl)methylene]-2-hydroxy benzohydrazide was synthesized and fully characterized. This complex is a pentacoordinate one in which the dioxo groups are in cis form. For synthesis of this complex, first, the intermediate compound 2-hydroxy benzohydrazide was synthesized from hydrazine and methyl salicylate and condensed with 2-hydroxynaphthaldehyde to give the Schiff base ligand (H2NBD). Then from reaction of ligand and ammonium vanadate in DMF in 65 ̊C, the NH4[VO2(NBD)] was prepared. This complex was fully characterized by UV, NMR and IR spectroscopies and it’s application as catalyst in sulfoxidation... 

    The use of a cis-dioxomolybdenum(VI) dinuclear complex with quadradentate 1,4-benzenediylbis(benzyldithiocarbamate)(2-) as model compound for the active site of oxo transfer molybdoenzymes: Reactivity, kinetics, and catalysis

    , Article Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy ; Volume 88 , 2012 , Pages 210-215 ; 13861425 (ISSN) Moradi Shoeili, Z ; Boghaei, D. M ; Sharif University of Technology
    2012
    Abstract
    Dinuclear cis-dioxomolybdenum(VI) complex [{MoO 2(Bz 2Benzenediyldtc)} 2] coordinated by a quadradentate dithiocarbamate (Bz 2Benzenediyldtc 2- = 1,4-benzenediylbis(benzyldithiocarbamate)(2-)) has been prepared and characterized by elemental analysis, 13C NMR, IR and UV-vis spectroscopy. The kinetics of the oxygen atom transfer between [{MoO 2(Bz 2Benzenediyldtc)} 2] and PPh 3 was studied spectrophotometrically in CH 2Cl 2 medium at 520 nm and four different temperatures, 288, 293, 298 and 303 K, respectively. The reaction follows second order kinetics with the rate constant k = 0.163(2) M -1 S -1 and its increasingly strong absorption at 520 nm clearly indicate the formation of a μ-oxo... 

    The synergistic effect of dimethyl sulfoxide vapor treatment and C60 electron transporting layer towards enhancing current collection in mixed-ion inverted perovskite solar cells

    , Article Journal of Power Sources ; Volume 405 , 2018 , Pages 70-79 ; 03787753 (ISSN) Saki, Z ; Aitola, K ; Sveinbjörnsson, K ; Yang, W ; Svanström, S ; Cappel, U. B ; Rensmo, H ; Johansson, E. M. J ; Taghavinia, N ; Boschloo, G ; Sharif University of Technology
    Elsevier B.V  2018
    Abstract
    Inverted perovskite solar cells (PSCs) have been introduced as better candidate for roll-to-roll printing and scale-up than their conventional configuration counterparts, while their fabrication is technically more demanding. The common light absorbing layer in inverted PSCs is the single cation methylammonium lead iodide (MAPbI3) perovskite, whereas mixed-ion perovskites are chemically more stable. In mixed-ion perovskites, where FA (formamidinium) is the main replacement for MA, the electron affinity is larger than in MAPbI3 perovskites, leading to possible barriers against photoelectron collection by the electron transporting layer (ETL). In this paper we report on a mixed-ion... 

    The LiClO4-mediated synthesis of β-(dialkylamino) sulfoxides and β- (dialkylamino) sulfones by addition of α-lithiated salts of sulfoxides and sulfones to aldehydes and (trimethylsilyl)dialkylamines

    , Article European Journal of Organic Chemistry ; Issue 9 , 2000 , Pages 1735-1739 ; 1434193X (ISSN) Naimi Jamal, M. R ; Ipaktschi, J ; Saidi, M. R ; Sharif University of Technology
    Wiley-VCH Verlag  2000
    Abstract
    The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding β-(dialkylamino) sulfoxides and β- (dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use  

    Synthesis and properties of novel fluorinated polyamides based on noncoplanar sulfoxide containing aromatic bis(ether amine)

    , Article Polymer Journal ; Volume 41, Issue 3 , 2009 , Pages 174-180 ; 00323896 (ISSN) Shockravi, A ; Abouzari Lotf, E ; Javadi, A ; Taheri, S ; Sharif University of Technology
    2009
    Abstract
    A novel sulfoxide containing bis(ether amine) monomer, 2,2'-sulfoxide- bis[4-methyl(2-trifluoromethyl)4-aminophenoxy) phenyl ether] (M2), was synthesized from the halogen displacement of 2-chloro-5-nitrobenzotrifluoride with dibenzosulfoxide (DH) in the presence of potassium carbonate, followed by catalytic reduction of bis(ether nitro) intermediate with Zinc/Ammonium chloride. A series of organic-soluble poly(ether amide)s (PA1-7) bearing sulfoxide and electronwithdrawing trifiuoromethyl group were synthesized from bis(ether amine) with various aromatic diacids (1-7) via a direct polycondensation with triphenyl phosphite and pyridine. The resulting polymers had inherent viscosities ranging... 

    Synthesis and characterization of magnetic silica-supported Mn(II)-substituted polyoxophosphotungstate as catalyst in sulfoxidation reaction

    , Article Journal of Nanoparticle Research ; Volume 18, Issue 10 , 2016 ; 13880764 (ISSN) Moradi Shoeili, Z ; Zare, M ; Bagherzadeh, M ; Sharif University of Technology
    Springer Netherlands  2016
    Abstract
    Abstract: Polyoxometalate-functionalized magnetic nanoparticles (Fe3O4@SiO2–MnPOW) were successfully synthesized via covalent anchoring of Mn(II)-substituted phosphotungstate on ammonium-modified Fe3O4@SiO2 nanoparticles. The complete characterization of nanoparticles has been carried out by scanning electron microscope, energy-dispersive X-ray, X-ray diffraction, Fourier transform infrared and elemental analysis. The resulting nanocomposites were efficient catalysts for the selective oxidation of sulfides with different green oxidants in good to excellent yields and also high selectivity. Leaching and recycling tests showed that the nanocatalyst can be reused several times without... 

    Synthesis, characterization and catalytic study of a novel iron(III)-tridentate Schiff base complex in sulfide oxidation by UHP

    , Article Inorganic Chemistry Communications ; Volume 12, Issue 1 , 2009 , Pages 21-25 ; 13877003 (ISSN) Bagherzadeh, M ; Amini, M ; Sharif University of Technology
    2009
    Abstract
    An hydrazone Schiff base-iron(III) complex using salicylidene benzoyl hydrazine (L) as ligand has been synthesized and characterized by elemental analyses, IR, 1H and 13C NMR and UV-Vis spectroscopy. Oxidation of sulfides to sulfoxides in one-step was conducted by this complex catalyst using urea hydrogen peroxide (UHP) in mixture of CH2Cl2/CH3OH (1:1) under air at room temperature. The effect of the reaction conditions on the oxidation of methylphenylsulfide was studied by varying the amount of the catalyst, reaction temperature, reaction time and the amount of UHP. The results showed that using this system in the oxidation of sulfides, sulfoxides were obtained as the main products,... 

    Spectral characterization of novel ternary zinc(II) complexes containing 1,10-phenanthroline and schiff bases derived from amino acids and salicylaldehyde-5-sulfonates

    , Article Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy ; Volume 67, Issue 3-4 , 2007 , Pages 944-949 ; 13861425 (ISSN) Boghaei, D. M ; Gharagozlou, M ; Sharif University of Technology
    2007
    Abstract
    A series of new ternary zinc(II) complexes [Zn(L1-10)(phen)], where phen is 1,10-phenanthroline and H2L1-10 = tridentate Schiff base ligands derived from the condensation of amino acids (glycine, l-phenylalanine, l-valine, l-alanine, and l-leucine) and salicylaldehyde-5-sulfonates (sodium salicylaldehyde-5-sulfonate and sodium 3-methoxy-salicylaldehyde-5-sulfonate), have been synthesized. The complexes were characterized by elemental analysis, IR, UV-vis, 1H NMR, and 13C NMR spectra. The IR spectra of the complexes showed large differences between νas(COO) and νs(COO), Δν (νas(COO) - νs(COO)) of 191-225 cm-1, indicating a monodentate coordination of the carboxylate group. Spectral data... 

    Solvent-free rapid microwave-assisted β-elimination of sulfoxides

    , Article Sulfur Letters ; Volume 24, Issue 6 , 2001 , Pages 269-273 ; 02786117 (ISSN) Matloubi Moghaddam, F ; Djamshidi, H ; Sharif University of Technology
    2001
    Abstract
    Basic silica gel (NaOH/SiO2) was found to be a very efficient media for the dehydrosulfenylation of sulfoxides in solvent-free condition under microwave irradiation  

    Solvent effects on kinetics of an heteroatomic nucleophilic substitution reaction in ionic liquid and molecular solvents mixtures

    , Article Russian Journal of Physical Chemistry A ; Volume 87, Issue 12 , 2013 , Pages 1969-1975 ; 00360244 (ISSN) Salari, H ; Pedervand, M ; Sadeghzadeh Darabi, F ; Gholami, M. R ; Sharif University of Technology
    2013
    Abstract
    Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25 C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the... 

    Single-centered hydrogen-bonded enhanced acidity (SHEA) acids: a new class of Bronsted acids

    , Article Journal of the American Chemical Society ; Volume 131, Issue 46 , 2009 , Pages 16984-16988 ; 00027863 (ISSN) Tian, Z ; Fattahi, A ; Lis, L ; Kass, S. R ; Sharif University of Technology
    2009
    Abstract
    Hydrogen bonds are the dominant motif for organizing the three-dimensional structures of biomolecules such as carbohydrates, nucleic acids, and proteins, and serve as templates for proton transfer reactions. Computations, gas-phase acidity measurements, and pKa determinations in dimethyl sulfoxide on a series of polyols indicate that multiple hydrogen bonds to a single charged center lead to greatly enhanced acidities. A new class of Brønsted acids, consequently, is proposed. © 2009 American Chemical Society  

    Preferential solvation and behavior of solvatochromic indicators in mixtures of an ionic liquid with some molecular solvents

    , Article The Journal of Physical Chemistry B ; vol.114 (29) , July , 2010 , pp 9586–9593 Salari, H. (Hadi) ; Khodadadi-Moghaddam, M.(Mohammad) ; Harifi-Mood, A. R. (Ali Reza) ; Gholami, M. R. (Mohammad Reza) ; Sharif University of Technology
    Abstract
    Structural and intermolecular interactions of solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardt’s dye were investigated in the binary mixtures of 2-hydroxy ethylammonium formate as an ionic liquid with N,N-dimethyl formamide, dimethyl amine, and dimethyl sulfoxide. Solvatochromic parameters (ETN, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen -bond donor acidity) were determined in ionic liquid mixtures at 25 °C using UV−vis spectroscopy. ETN parameters obtained from absorbance of Reichardt’s dye within various mixtures of ionic liquid were observed to be higher than predicted values from ideal additive... 

    Preferential solvation and behavior of solvatochromic indicators in mixtures of an ionic liquid with some molecular solvents

    , Article Journal of Physical Chemistry B ; Volume 114, Issue 29 , 2010 , Pages 9586-9593 ; 15206106 (ISSN) Salari, H ; Khodadadi Moghaddam, M ; Harifi Mood, A. R ; Gholami, M. R ; Sharif University of Technology
    American Chemical Society  2010
    Abstract
    Structural and intermolecular interactions of solvatochromic probes 4-nitroaniline, 4-nitroanisole, and Reichardts dye were investigated in the binary mixtures of 2-hydroxy ethylammonium formate as an ionic liquid with N,N-dimethyl formamide, dimethyl amine, and dimethyl sulfoxide. Solvatochromic parameters (ETN, normalized polarity parameter; π, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen -bond donor acidity) were determined in ionic liquid mixtures at 25°C using UV-vis spectroscopy. ETN parameters obtained from absorbance of Reichardt dye within various mixtures of ionic liquid were observed to be higher than predicted values from ideal additive behavior.... 

    Polymeric ionic liquid nanogel-anchored tungstate anions: A robust catalytic system for oxidation of sulfides to sulfoxides

    , Article New Journal of Chemistry ; Volume 39, Issue 2 , 2015 , Pages 1348-1354 ; 11440546 (ISSN) Pourjavadi, A ; Nazari Chamazkoti, M ; Hosseini, S. H ; Sharif University of Technology
    Abstract
    A new heterogeneous catalytic system was prepared by immobilization of tungstate ions on a cross-linked poly(ionic liquid) nanogel. The solid nanogel was easily synthesized by a surfactant-less method. The resulting catalyst was highly active in selective oxidation of sulfides to sulfoxides by H2O2. The oxidation reactions were successfully performed under solvent-free conditions affording high yields. The catalyst was recycled and reused for several reaction cycles without any significant loss of catalytic activity