- Synthesis, X-ray structure, DFT studies, and catalytic activity of a vanadium(V) complex containing a tridentate Schiff base
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Reactions of a solution of NH4VO3 in H 2O2 and water and salicylidene benzoyl hydrazine as a tridentate Schiff base (ONO) afford a six-coordinate V(V) complex [VO(ONO)(OCH3)(CH3OH)] with a distorted octahedral configuration. The complexes [VO(ONO)(OCH3)(CH3OH)] were isolated as air-stable crystalline solids and fully characterized, including by single-crystal X-ray structure analysis. DFT calculations have been performed to understand the electronic structure of the complex. Vibrational frequencies and maximum absorption wavelengths of the complex theoretically calculated are in good agreement with experimental values. [VO(ONO)(OCH3)(CH 3OH)] shows efficient oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide as the oxidant at room temperature under air.
- Amini, Mojtaba,Arab, Ali,Soleyman, Rouhollah,Ellern, Arkady,Woo, L. Keith
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- Oxidation of sulfides with urea-hydrogen peroxide catalyzed by iron-salen complexes
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The oxidation of sulfides to sulfoxides with hydrogen peroxide in good yield and high selectivity has been catalyzed very effectively by a series of Schiff base salen-type iron complexes in a monophasic medium (CH 2Cl2/CH3OH) at ambient temperature. The results of the present study show that the reaction rate strongly depends on both catalyst steric effects and steric and electronic properties of sulfides. In the system, the electronic spectral studies are applied to explain the formation of a reactive (salen) Fe=O intermediate.
- Bagherzadeh, Mojtaba,Zare, Maryam
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- Polysiloxane-supported fullerene derivative as a new heterogeneous sensitiser for the selective photooxidation of sulfides to sulfoxides by 1O2
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A heterogeneous photosensitiser for the generation of singlet oxygen was synthesized by covalent attachment of a methanofullerene derivative to polysiloxane-based Deloxan DAP beads and its performance in the photooxidation of sulfides to sulfoxides was investigated. As opposed to C60 and many of its derivatives, the heterogeneous sensitiser can be readily used in protic solvents such as methanol which makes the photooxygenation highly selective, affording good to excellent yields of sulfoxides with aliphatic and benzylic sulfides. Moreover, the sensitiser is easily recovered at the end of the reaction by simple filtration.
- Latassa, Daniel,Enger, Olivier,Thilgen, Carlo,Habicher, Tilo,Offermanns, Heribert,Diederich, Francois
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- Nanoparticle supported, magnetically separable vanadium complex as catalyst for selective oxidation of sulfides
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A magnetically recyclable vanadium(V) catalyst was synthesized by covalent anchoring of VO(salen)Cl on silica-coated Fe3O4 nanoparticles. This straightforward preparation yields magnetically separable Fe3O4@SiO2@VO(salen) nanoparticles with high vanadium loading. 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.
- Bagherzadeh, Mojtaba,Haghdoost, Mohammad Mehdi,Shahbazirad, Ayoob
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- Synthesis, x-ray studies, and catalytic activity of tridentate schiff base dioxo-molybdenum(VI)
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The reaction of a solution of MoO2(acac)2 in CH3OH and salicylidene 2-picoloyl hydrazone as a tridentate ONO donor Schiff base (ONO) afford a six-coordinated Mo(VI) complex [MoO2(ONO) (CH3OH)], with a distorted octahedral configuration. [MoO2(ONO)(CH3OH)] was isolated as an airstable crystalline solid and fully characterized by single-crystal X-ray structure analysis. [MoO2(ONO)(CH3OH)] shows reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide as the oxidant at room temperature under air.
- Amini, Mojtaba,Khaksar, Mostafa,Boghaei, Davar M.,Bagherzadeh, Mojtaba,Ellern, Arkady,Keith Woo
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- A novel 12-molybdovanadate nanocluster: Synthesis, structure investigation and its application as an efficient heterogeneous sulfoxidation catalyst
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Tetraethylammonium salt of a new Keggin-type 12-molybdovanadate nanocluster, [(C2H5)4N]4[VMo12O40] (1) was synthesized via reaction between sodium tungstate, ammonium vanadate and tetraethylammonium bromide in acidic medium. Compound 1 was characterized by X-ray crystallography, FT-IR, UV–Vis and cyclic voltammetry and then applied as an efficient heterogeneous catalyst to oxidation of various organosulfides to sulfoxides with H2O2 at room temperature with 81–100% conversion and 60–99% selectivity. Nanocluster 1 was also shown to display excellent recyclability – it can be reused more than 10 times.
- Amini, Mojtaba,Sheykhi, Ayda,Naslhajian, Hadi,Bayrami, Arshad,Bagherzadeh, Mojtaba,Ho?yńska, Ma?gorzata
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- Mo(vi) complex supported on Fe3O4 nanoparticles: magnetically separable nanocatalysts for selective oxidation of sulfides to sulfoxides
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A molybdenum complex, [MoO2Cl2(DMSO)2], was immobilized on amino propyl and Schiff base modified magnetic Fe3O4@SiO2 nanoparticles by covalent linkage. The resulting nanoparticles were used as efficient and recyclable catalysts for the selective oxidation of sulfides to sulfoxides using urea hydrogen peroxide as the oxidant. The complete characterization of catalysts was carried out by means of thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), elemental analysis, FT-IR and Raman microprobe techniques.
- Keypour, Hasan,Balali, Masomeh,Haghdoost, Mohammad Mehdi,Bagherzadeh, Mojtaba
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- New mononuclear manganese(II) complexes with 2,4,6-tris(2-pyridyl)-1,3,5- triazine (tptz) - Selective catalyst in UHP oxidation of sulfides
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A new manganese complex of the formula [Mn(tptz)(OH2) 3](CF3SO3)2·EtOH, (1, where tptz = (2,4,6-tris(2-pyridyl)-1,3,5-triazine) is presented, exhibiting an excellent catalytic activity and selectivity in oxidation of various sulfides to the corresponding sulfoxides with UHP (urea hydrogen peroxide) as oxidant under air at room temperature. A modified preparation procedure produces another new manganese complex of the formula [Mn(tptz)(CH3COO)(OH 2)2](CF3SO3)·3H2O (2). X-ray structures of both Mn(II) complexes, properties (elemental analysis, electrochemistry, EPR, IR, Raman, and UV-Vis spectra), as well as DFT studies results are reported.
- Najafpour, Mohammad Mahdi,Holynska, Malgorzata,Shamkhali, Amir Nasser,Amini, Mojtaba,Kazemi, Sayed Habib,Zaynalpoor, Sasan,Mohamadi, Rahim,Bagherzadeh, Mojtaba,Lis, Tadeusz
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- Nanolayered manganese-calcium oxide as an efficient catalyst toward organic sulfide oxidation
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We for the first time report that nanolayered Mn-Ca oxide in the presence of H2O2 is an efficient catalyst toward sulfide oxidation to sulfoxide. We characterized the catalyst by DLS, UV-Vis, diffuse reflectance infrared Fourier transform spectroscopy, SEM, TEM and HRTEM. We also considered different parameters of the sulfide-oxidation reaction.
- Amini, Mojtaba,Najafpour, Mohammad Mahdi,Naslhajian, Hadi,Amini, Emad,Farnia, S. Morteza F.
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- Synthesis and characterization of molybdenum complex supported on magnetic and non-magnetic supports: comparing their catalytic activity, selectivity, and reusability
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A molybdenum complex was immobilized on Schiff-base-modified magnetic and non-magnetic particles by covalent linkage. The characterizations of the obtained materials were carried out by means of TG–DTG, SEM, TEM, VSM, XPS, IR, and Raman microprobe techniques. All of them exhibited efficient activities in the oxidation of sulfides to sulfoxides by urea hydrogen peroxide oxidant. The advantages and disadvantages of these catalysts are discussed in detail. Molybdenum complex immobilized on silica bead can be recycled and recovered by simple filtration, but it demonstrated low activity in catalytic oxidation reaction. Immobilization on nano-SiO2 leads to the formation of nanocatalyst having high catalytic activity but inefficient reusability. The best results were obtained with nano-Fe3O4 magnetic support. The immobilized molybdenum complex on silica-coated magnetic nanoparticles can easily be recovered from the reaction system using an external magnet and reused several times with high yields.
- Bagherzadeh, Mojtaba,Balali, Masomeh,Haghdoost, Mohammad Mehdi,Keypour, Hassan
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- Solvent effects in the oxidation of sulfides with NaBrO 3/Mg(HSO4)2
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The oxidation of alkyl and aryl sulfides into the corresponding sulfoxides by NaBrO3/Mg(HSO4)2 is studied. The selectivity of the reactions are highly governed by the choice of solvents and reaction conditions. Both alkyl and aryl sulfides are efficiently oxidized in CH3CN and under solvent-free conditions, but in competition reactions with alkyl and aryl sulfides in CH3CN only alkyl sulfides are oxidized. In n-hexane alkyl sulfides are oxidized to sulfoxides and oxidation of aryl sulfides completely inhibited.
- Shaabani, Ahmad,Bazgir, Ayoob,Soleimani, Kamal,Salehi, Peyman
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- Oxido-peroxido W(VI)-histidine–MgAl-layered double hydroxide composite as an efficient catalyst in sulfide oxidation
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Oxido-peroxido W(VI)-histidine–MgAl-layered double hydroxide composite was prepared by using MgAl-layered double hydroxide as a host and oxido-peroxido W(VI)-histidine complex as a guest. The composite was characterized by XRD, IR, EDX,SEM and TEM techniques. This composite is tested for catalytic selective sulfoxidation reactions using hydrogen peroxide as oxidant showing good to moderate conversion along with high selectivity.
- Nikkhoo, Mohammad,Amini, Mojtaba,Morteza,Farnia,Bayrami, Arshad,Bagherzadeh, Mojtaba,Gautam, Sanjeev,Chae, Keun Hwa
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- A water-oxidizing dinuclear iron complex as an efficient catalyst toward organic sulfide oxidation
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In this paper, we report that a known dinuclear Fe complex, [tpa(H2O)FeOFe(H2O)tpa](ClO4)4 (tpa: tris(2-pyridylmethyl)amine), is an efficient catalyst toward organic sulfide oxidation in the presence of urea-hydrogen peroxide.
- Amini, Mojtaba,Najafpour, Mohammad Mahdi,Zare, Maryam,Holyska, Malgorzata,Moghaddam, Atefeh Nemati,Bagherzadeh, Mojtaba
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- A simple and efficient procedure for oxidation of sulfides to sulfoxides by hexamethylenetetramine-bromine complex(HMTAB)
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Hexamethylenetetramine-bromine has been found to be an efficient and selective reagent for the oxidation of sulfides to the corresponding sulfoxides.
- Shaabani,Teimouri,Safaei
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- Selective oxidation of organosulfurs with a sandwich-type polyoxometalate/hydrogen peroxide system
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A dimeric tungstophosphate, Na14[Co4(PW9O35)2].28H2O (1), was synthesized via a simple one-pot method and characterized by single-crystal X-ray crystallography. Nanocluster 1 was exhibited to be able to selective oxidation of aliphatic and aromatic sulfides to sulfoxides in the presence of hydrogen peroxide at room temperature with high performance. Further investigations showed that this catalyst could reuse four times without a significant reduction in its activity for the oxidation of methyl phenyl sulfide.
- Amin Dastyar, Mohammad,Amini, Mojtaba,Bagherzadeh, Mojtaba,Bayrami, Arshad,Janczak, Jan,Morteza F. Farnia, S.,Naslhajian, Hadi
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- Synthesis and characterization of two binuclear nickel(II) complexes of thiophenol-based "end-off" compartmental ligands and their application as catalysts for selective oxidation of sulfides
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Reaction of the binucleating S-protected ligand precursors 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy anil (I) and 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy 5′-methyl anil (II) with nickel(II) acetate tetrahydrate in the presence of pyrazole afforded the binuclear nickel(II) complexes [LINi2(pz)] (1) and [LIINi2(pz)] (2), respectively. The complexes have been characterized by routine physicochemical studies as well as by X-ray single crystal structure analysis. In both complexes, Ni(II) ions are doubly bridged by the thiophenolic sulfur of the pentadentate Schiff base ligand and a pyrazolate group. Efficient protocols for the oxidation of sulfides to sulfoxides with high selectivities, catalyzed by binuclear -thiophenolato - pyrazolatonickel(II) in the presence of urea hydrogen peroxide (UHP) were explored. We obtained predominantly the monooxygenated product. The resulting products are obtained in good to excellent yields within a reasonable time.
- Khadir, Narjes,Amini, Mojtaba,Assoud, Abdeljalil,Bagherzadeh, Mojtaba,Boghaei, Davar M.
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- Catalytic oxidation of organic sulfides by new iron-chloro Schiff base complexes: The effect of methoxy substitution and ligand isomerism on the electronic, electrochemical and catalytic performance of the complexes
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Four new Fe(III)-Chloro Schiff base complexes were synthesized and characterized. The N2O2 type tetradentate Schiff base ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with salicylaldehyde (H2L1), 3-methoxysalicylaldehyde (H2L2), 4-methoxysalicylaldehyde (H2L3) and 5-methoxysalicylaldehyde (H2L4). The corresponding iron-chloro complexes with the general formula [Fe(Ln)Cl] (n = 1–4 for complexes (1–4)) were characterized by FTIR and UV–Vis spectroscopy and elemental analysis. Crystal structure of (1) was obtained by single-crystal X-ray crystallography. Cyclic voltammetry was used to study the electrochemistry of the complexes. The complexes were used as catalysts for the selective oxidation of organic sulfide compounds to sulfoxides. High catalytic performance and selectivity were obtained. The spectroscopic, electrochemical and catalytic data are discussed based on the electronic, steric and electrochemical properties of the complexes.
- Aghvami, Fatemeh,Ghaffari, Abolfazl,Kucerakova, Monika,Dusek, Michal,Karimi-Nami, Rahman,Amini, Mojtaba,Behzad, Mahdi
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- Synthesis, characterization, DFT studies and catalytic activities of manganese(ii) complex with 1,4-bis(2,2′:6,2′′-terpyridin- 4′-yl) benzene
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A new di-manganese complex with "back-to-back" 1,4-bis(2,2′:6,2′′-terpyridin-4′-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electron located on oxyl-ligand emphasizes the radical mechanism of water oxidation for the system.
- Najafpour,Hillier,Shamkhali,Amini,Beckmann,Jagli?i?,Jagodi?,Strauch, Peter,Moghaddam, A. Nemati,Beretta,Bagherzadeh
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- Synthesis, X-ray studies, DFT calculations and catalytic activity of a novel iron complex containing an N, O-type bidentate oxazine ligand
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The reactions of FeCl3·3H2O and 2-(2′-hydroxyphenyl)-5,6-dihydro-1,3-oxazine (N-O) as a bidentate O, N donor ligand afforded a five-coordinated iron(III) complex, [Fe(N-O) 2Cl], with a distorted trigonal bipyramidal configuration. The complex [Fe(N-O)2Cl] was isolated as an air-stable crystalline solid and was fully characterized, including by single-crystal X-ray structure analysis. The complex [Fe(N-O)2Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature under air. To get an insight into the electronic structure of the complex, the experimental studies have been accompanied by density functional theory (DFT) computations.
- Amini, Mojtaba,Haghdoost, Mohammad Mehdi,Bagherzadeh, Mojtaba,Ellern, Arkady,Woo, L. Keith
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- A hexanuclear manganese(ii) complex: Synthesis, characterization and catalytic activity toward organic sulfide oxidation
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Herein we report on the synthesis and characterization of a hexanuclear [MnII6] wheel-like assembly with naphthalene-1,8-dicarboxylate and 1,10-phenanthroline as ligands. Overall antiferromagnetic behavior of the magnetic properties is observed. The complex acts as a catalyst toward organic sulfide oxidation in the presence of H2O2 with good selectivity (98-100%). This journal is
- Najafpour, Mohammad Mahdi,Amini, Mojtaba,Holyska, Malgorzata,Zare, Maryam,Amini, Emad
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- Greener Preparation of 5-Ethyl-4a-hydroxyisoalloxazine and Its Use for Catalytic Aerobic Oxygenations
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Isoalloxazine ring systems are found in flavin cofactors in nature, and the simulation of their redox catalyses is an important task for developing sustainable catalytic oxidation reactions. Although 5-ethyl-4a-hydroxyisoalloxazines are among the most promising candidates as catalyst for such purposes, the use of them for laboratorial as well as industrial synthetic chemistry has so far been quite limited presumably due to the lack of their preparation methods readily, safely, and inexpensively available. In this communication, we introduce an environmentally benign and practical preparation of 5-ethyl-4a-hydroxy-3,7,8,10-tetramethylisoalloxazine (1EtOH) from 3,7,8,10-tetramethylisoalloxazine (1), in which conventional synthetic requirements, including (i) operations under inert conditions, (ii) risky or expensive chemicals, and (iii) isolation of labile intermediates, have all been dissolved. In addition, we have presented that 1EtOH could be an effective catalyst for Baeyer–Villiger oxidation as well as sulfoxidation with molecular oxygen (O2) as a terminal oxidant under suitable conditions, which is the first report on aerobic oxygenations catalyzed by 5-alkyl-4a-hydroxyisoalloxazines.
- Oonishi, Takahiro,Kawahara, Takayuki,Arakawa, Yukihiro,Minagawa, Keiji,Imada, Yasushi
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p. 1791 - 1795
(2019/02/07)
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- Heterogeneous viologen catalysts for metal-free and selective oxidations
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Metal-free oxidation, a green chemistry process, has drawn significant attention from catalysis researchers. However, most oxidation processes are completed by homogeneous metal-free catalysts, whereas heterogeneous metal-free materials have been developed with limited successes. In this study, polymerized ionic networks (PINs) with N,N′-dialkyl-4,4′-bipyridinium units as heterogeneous viologen type of catalysts exhibited high efficiency in the oxidation of aromatic sulfides/alcohols to sulfoxides/aldehydes, respectively (conversion: >90%, selectivity: >95%). The catalytic performance of PINs originates from the electron-accepting ability of the viologen unit, which can reduce H2O2 into an active species. Especially, the synthesis of PIN catalysts is a one-step simple polymerization reaction between benzyl bromide and bipyridine in air. The metal-free heterogeneous feature, high selectivity, mild conditions (60 °C, 1 h), and the facile preparation of the catalyst make the current selective oxidation approach attractive.
- Hou, Shengtai,Chen, Nanqing,Zhang, Pengfei,Dai, Sheng
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supporting information
p. 1455 - 1460
(2019/03/26)
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- Oxidation of sulfides using recyclable pseudocyclic benziodoxole triflate
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A new pseudocyclic hypervalent iodine reagent, benziodoxole triflate (IBA-OTf, a complex of 2-iodosylbenzoic acid with trifluoromethanesulfonic acid), can be used as an efficient oxidant for selective oxidation of various organic sulfides to sulfoxides. This oxidation proceeds under mild condition to afford the corresponding sulfoxides in moderate to good yields without overoxidation. The reduced form of the hypervalent iodine reagent, 2-iodobenzoic acid, can be easily recovered from the reaction mixture in good yields by a simple acid-base liquid-liquid biphasic protocol. (Chemical Equation Presented).
- Yoshimura, Akira,Zhdankin, Viktor V.
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- Catalytic behavior of an iron(III) complex containing an N,O-type bidentate oxazoline ligand for selective oxidation of sulfides
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The reaction of Fe(acac)3 and 2-(2′-hydroxyphenyl)oxazoline (Hphox) as a bidentate O,N donor ligand afforded a six-coordinated iron(III) complex [Fe(phox)2(acac)] with distorted octahedral configuration. The complex was isolated as an air-stable crystalline solid and characterized by elemental analysis, FTIR, solution electrical conductivity, and by single-crystal X-ray structure analysis. The structure, electronic properties, and vibrational normal modes of the complex were investigated by DFT. The use of this complex as a catalyst for the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide as the primary oxidant was investigated. The catalyst shows very efficient reactivity, giving high yields and selectivities at room temperature under air.
- Amini, Mojtaba,Khaksar, Mostafa,Arab, Ali,Jahandizi, Reza Masoomi,Bagherzadeh, Mojtaba,Boghaei, Davar M.,Ellern, Arkady,Keith Woo
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- Selective Oxidation of Sulfides Catalyzed by the Nanocluster Polyoxomolybdate (NH4)12[Mo36(NO)4O108(H2O)16]
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The (NH4)12[Mo36(NO)4O108(H2O)16]·30.84H2O ({Mo36}) catalyst has been synthesized and successfully employed in the selective oxidation of various sulfides to sulfoxides with urea hydrogen peroxide as oxidant under mild reaction conditions with 84-99 % conversion and 58-99 % selectivity, with active functional groups such as the hydroxy group and C=C bonds tolerated in the oxidation. The {Mo36} catalyst showed high catalytic activity for a high substrate/catalyst ratio (up to 30000:1) and is recyclable.
- Amini, Mojtaba,Naslhajian, Hadi,Farnia, S. Morteza F.,Holyska, Malgorzata
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p. 3873 - 3878
(2015/08/24)
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- Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions
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Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0-1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions.
- Kon, Yoshihiro,Yokoi, Toshiyuki,Yoshioka, Masato,Tanaka, Shinji,Uesaka, Yumiko,Mochizuki, Takehisa,Sato, Kazuhiko,Tatsumi, Takashi
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p. 7584 - 7592
(2014/12/10)
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- Selective oxidation of sulfides to sulfoxides with cyanuric chloride and urea-hydrogen peroxide adduct
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Although a number of methods have been developed for the selective oxidation of sulfides to sulfoxides, the need remains for alternative efficient, reliable strategies that can be generally applied to various sulfides and that use readily available reagents under mild reaction conditions. Herein, we report the use of urea-hydrogen peroxide adduct (UHP) and cyanuric chloride in CH 3CN at room temperature to convert sulfides to sulfoxides in excellent yields. In particular, this protocol produced sulfoxides with aromatic rings bearing electron-withdrawing groups in excellent yields.
- Jeon, Heung Bae,Kim, Kyoung Tae,Kim, Sang Hyun
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p. 3905 - 3908
(2014/07/08)
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- Synthesis, structural, spectral, electrochemical and catalytic properties of VO (IV) complexes containing N, O donors
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Complexes of the general formula M (X-DPMP)2[where, (M = VOIV), DPMP = 2-[(2,6-Diisopropyl-phenylimino)-methyl]-phenol and X = Br, BrCl, Ph] have been synthesized and characterized by IR, electronic, ESR spectral, magnetic and cyclic voltammetry measurements. The newly synthesized Schiff bases act as monobasic bidentate ligand in their complexes. The spectral data indicate that the ligand coordinates through the phenolic oxygen and azomethine nitrogen atoms. The observed parameters, hyperfine splitting constant (A) and Landé splitting energy (g) are found to be in good agreement with the values generally observed for the vanadyl complex with square pyramidal geometry. The cyclic voltammetric redox potentials of VO (IV) complexes suggest the existence of irreversible pairs in acetonitrile. The vanadium complexes were screened for sulfide oxidation studies and VO (C19H21BrON)2or [VO (Br-DPMP)2] was found to be an efficient catalyst for the oxidation of various sulfides to sulfoxides with PhIO terminal oxidant. Both aryl and alkyl sulfides were selected and converted into sulfoxides in good to excellent yields.
- Kanmani Raja,Lekha,Hariharan,Easwaramoorthy,Rajagopal
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p. 227 - 233
(2014/12/10)
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- Synthesis, X-ray studies, and catalytic efficacy of a novel iron complex containing an N,O-type bidentate thiazoline ligand
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The reactions of FeCl3·6H2O and 2-(2′-hydroxyphenyl)-2-thiazoline as a bidentate O-N donor thiazoline ligand (thoz) afford a five-coordinate FeIII complex [Fe(thoz) 2Cl] with a distorted square pyramidal configuration. Complex [Fe(thoz)2Cl] was isolated as air-stable crystalline solids and fully characterized, including by single-crystal X-ray structure analysis. Complex [Fe(thoz)2Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature in air. Copyright
- Amini, Mojtaba,Bigdeli, Mina,Delsouz-Hafshejani, Sepideh,Ellern, Arkady,Woo, L. Keith
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p. 385 - 389
(2014/03/21)
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- Molybdenum(VI)-oxodiperoxo complex containing an oxazine ligand: Synthesis, X-ray studies, and catalytic activity
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A new mononuclear molybdenum(VI)-oxodiperoxo complex [MoO(O 2)2(phox)] with a simple bidentate ligand, 2-(2′-hydroxyphenyl)-5,6-dihydro-1,3-oxazine (Hphox), has been synthesized and characterized by X-ray structure analysis, elemental analysis, infrared, and 1H NMR spectroscopy. A triclinic space group P-1 was determined by X-ray crystallography from single-crystal data of this complex. The resulting complex functioned as a facile sulfide oxidation catalyst with urea hydrogen peroxide as terminal oxidant at room temperature. The catalyst showed efficient reactivity in oxidation of sulfides giving high yield and selectivity.
- Amini, Mojtaba,Bagherzadeh, Mojtaba,Atabaki, Behnam,Derakhshandeh, Parviz Gohari,Ellern, Arkady,Woo, L. Keith
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p. 1429 - 1436
(2014/07/08)
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- A novel iron complex containing an N,O-type bidentate oxazoline ligand: Synthesis, X-ray studies, DFT calculations and catalytic activity
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A five-coordinated Fe(III) complex with the distorted trigonal bipyramidal configuration was synthesized by reactions of FeCl36H2O and 2-(2′-hydroxyphenyl)oxazoline (Hphox) as a bidentate ON donor oxazoline ligand. Complex [Fe(phox)2Cl] was fully characterized, including by single-crystal X-ray structure analysis. DFT calculations were accompanied with experimental results in order to obtain a deeper insight into the electronic structure and vibrational normal modes of complex. Oxidation of sulfides to sulfoxides in one-step was conducted by this complex as catalyst using urea hydrogen peroxide (UHP) in mixture of CH2Cl 2/CH3OH (1:1) under air at room temperature. The results show that using this system in oxidation of sulfides, sulfoxides are obtained as the main products, together with variable amounts of sulfones (≤13%), depending on the nature of the substrate.
- Amini, Mojtaba,Arab, Ali,Derakhshandeh, Parviz Gohari,Bagherzadeh, Mojtaba,Ellern, Arkady,Woo, L. Keith
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p. 432 - 438
(2014/07/08)
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- Selective oxidation of bulky sulfides to sulfoxides over titanosilicates having an MWW structure in the presence of H2O2 under organic solvent-free conditions
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A selective hydrogen peroxide oxidation of sulfides to sulfoxides using Ti-MWW and Ti-IEZ-MWW catalysts was developed. This reaction was carried out under organic solvent-free conditions, and the only side-product was water. Improvement of catalytic activity toward bulky sulfides will be achieved by optimization of the topology in the Ti zeolite.
- Kon, Yoshihiro,Yokoi, Toshiyuki,Yoshioka, Masato,Uesaka, Yumiko,Kujira, Harumi,Sato, Kazuhiko,Tatsumi, Takashi
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supporting information
p. 4918 - 4921
(2013/09/02)
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- Selective oxidation of sulfides and olefins by a manganese (III) complex containing an N,O-type bidentate oxazine ligand
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A new manganese(III) complex [(N-O)2Mn(OAc)] was synthesized using 2-(2'-hydroxyphenyl)-5,6-dihydro-1,3-oxazine (N-O) as a bidentate O, N donor. The complex has been characterized by elemental analysis, IR, UV-vis spectroscopy, and X-ray structure analysis. Oxidation of sulfides and epoxidation of olefins, respectively, to their corresponding sulfoxides and epoxides were conducted by this catalyst using urea hydrogen peroxide as oxidant at room temperature under air. The catalyst is efficient in oxidation reactions giving high yields and selectivities.
- Amini, Mojtaba,Bagherzadeh, Mojtaba,Moradi-Shoeili, Zeinab,Boghaei, Davar M.,Ellern, Arkady,Woo, L. Keith
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p. 464 - 472
(2013/08/24)
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- Flavin-catalyzed aerobic oxidation of sulfides in aqueous media
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An aerobic, organocatalytic, and aqueous method for the oxidation of sulfides is described. Synthetic flavin, 5-ethyl-3,7,8,10- tetramethylisoalloxazinium perchlorate, acts as an efficient catalyst for the oxidation of sulfides in water under an oxygen atmosphere (1 atm) with the assistance of ascorbic acid as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides.
- Imada, Yasushi,Kitagawa, Takahiro,Wang, Han-Kun,Komiya, Naruyoshi,Naota, Takeshi
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p. 621 - 624
(2013/02/23)
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- Aerobic oxidation of sulfides with a vitamin B2-derived organocatalyst
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5-Ethyl-3-methyl-2′,4′:3′,5′-di-O-methylenedioxy- riboflavinium perchlorate (DMRFlEt+ClO4-) is readily derived from commercially available vitamin B2 (riboflavin) and exhibits high catalytic activity for the oxidation of organic sulfides under an oxygen atmosphere (1 atm) with the assistance of hydrazine hydrate as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides. Georg Thieme Verlag Stuttgart New York.
- Imada, Yasushi,Tonomura, Itoko,Komiya, Naruyoshi,Naota, Takeshi
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supporting information
p. 1679 - 1682
(2013/09/02)
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- Oxidation of sulfides with hydrogen peroxide catalyzed by vitamin B 2 derivatives
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5-Ethyl-3-methyl-2′,4′:3′,5′-di-O- methylenedioxyriboflavinium perchlorate (1, DMRFlEt+ClO4 -), derived readily from commercially available vitamin B2 (riboflavin), exhibits high catalytic activity for the oxidation of organic sulfides with hydrogen peroxide. The reaction provides an efficient and selective method for the oxidative transformation of organic sulfides to the corresponding sulfoxides under mild conditions.
- Imada, Yasushi,Takagishi, Masamitsu,Komiya, Naruyoshi,Naota, Takeshi
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p. 3064 - 3071
(2013/09/12)
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- Catalytic efficacy of an oxido-peroxido tungsten(VI) complex: Synthesis, X-ray structure and oxidation of sulfides and olefins
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An oxido-peroxido tungsten(VI) complex [WO(O2)L(CH 30H)] using salicylidene benzoyl hydrazine as a tridentate ONO donor Schiff base (H2L) has been synthesized and characterized by elemental analysis, IR, 1H NMR, molar conductance data, and single-crystal X-ray analysis. The complex was used as a catalyst for epoxidation of olefins and oxidation of sulfides. The results show that epoxides and sulfoxides were produced in high yield, turnover number, and selectivity.
- Amini, Mojtaba,Bagherzadeh, Mojtaba,Eftekhari-Sis, Bagher,Ellern, Arkady,Woo, L. Keith
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p. 1897 - 1905
(2013/07/28)
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- Molybdenum oxo-peroxo complex: A very fast catalyst for oxidation and reduction of sulfur-based compounds
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We have evaluated the catalytic activity of a molybdenum(VI) oxo-peroxo complex through the oxidation and reduction of sulfur-based compounds. Arylalkyl, diaryl and dialkyl sulfides are selectively oxidized to corresponding sulfoxides, with tert-butyl hydroperoxide (TBHP), in the presence of MoO(O 2)(phox)2 complex as catalyst. This molybdenum complex was also found to be an efficient catalyst for the deoxygenation of sulfoxides to sulfides with PPh3 in excellent yields and chemoselectivity.
- Bagherzadeh, Mojtaba,Haghdoost, Mohammad Mehdi,Amini, Mojtaba,Derakhshandeh, Parviz Gohari
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experimental part
p. 14 - 19
(2012/06/16)
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- Preparation, X-ray structure, and reactivity of 2-iodylpyridines: Recyclable hypervalent iodine(V) reagents
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2-Iodylpyridine and four examples of 3-alkoxy-2-iodylpyridines were prepared by oxidation of the respective 2-iodopyridines with 3,3-dimethyldioxirane. Structures of 2-iodylpyridine, 2-iodyl-3- isopropoxypyridine, and 2-iodyl-3-propoxypyridine were established by single-crystal X-ray diffraction analysis. 2-Iodyl-3-propoxypyridine has moderate solubility in organic solvents (e.g., 1.1 mg/mL in acetonitrile) and can be used as a recyclable reagent for oxidation of sulfides and alcohols. The reduced form of this reagent, 2-iodo-3-propoxypyridine, can be effectively separated from the reaction mixture by treatment with diluted sulfuric acid and recovered from the acidic aqueous solution by adding aqueous sodium hydroxide.
- Yoshimura, Akira,Banek, Christopher T.,Yusubov, Mekhman S.,Nemykin, Victor N.,Zhdankin, Viktor V.
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experimental part
p. 3812 - 3819
(2011/07/08)
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- Synthesis, X-ray structure, characterization and catalytic activity of a polymeric manganese(II) complex with iminodiacetate
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A polymeric manganese(II) complex with the general formula [Mn(O 2CCH2NH2CH2CO2) 2(H2O)2]n from reaction of iminodiacetatic acid and manganese(II) perchlorate under nitrogen in water, was synthesized and characterized. The structure of the complex was determined using single-crystal X-ray diffraction, elemental analysis, IR and UV-vis spectra. This complex exhibited excellent catalytic activity and selectivity for oxidation of various alcohols and sulfides to the corresponding aldehydes/ketone and sulfoxides using urea hydrogen peroxide and oxone (2KHSO 5·KHSO4·K2SO4), respectively, as oxidants under air at room temperature. The easy preparation, mild reaction conditions, high yields of the products, short reaction time, no over-oxidation products, high selectivity and inexpensive system make this catalytic system a useful method for oxidizing various alcohols and sulfides. Copyright
- Bagherzadeh, Mojtaba,Amini, Mojtaba,Boghaei, Davar M.,Najafpour, Mohammad Mahdi,McKee, Vickie
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experimental part
p. 559 - 563
(2012/04/04)
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- Oligomeric iodosylbenzene sulfate: A convenient hypervalent iodine reagent for oxidation of organic sulfides and alkenes
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Oligomeric iodosylbenzene sulfate, (PhIO)3·SO 3, which can be formally considered as a partially depolymerized activated iodosylbenzene, is a readily available, stable, and water-soluble hypervalent iodine reagent that is useful for the oxidation of sulfides or alkenes. Furthermore, this reagent can be conveniently generated in situ from (diacetoxyiodo)benzene and sodium bisulfate and used without isolation in oxidations in aqueous solution or under solvent-free conditions. The reaction of iodosylbenzene sulfate in situ with organic sulfides at room temperature affords sulfoxides in high yields without over-oxidation to sulfones, and this reaction is compatible with the presence in the substrate molecule of hydroxy groups, double bonds, benzylic carbon atoms, carboxylate groups, and various substituted phenyl rings. The reaction of an alkene with iodosylbenzene sulfate generated in situ results in oxidative rearrangement to form a ketone or aldehyde. Georg Thieme Verlag Stuttgart.
- Yusubov, Mehman S.,Yusubova, Rosa Y.,Funk, Tatyana V.,Chi, Ki-Whan,Zhdankin, Viktor V.
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experimental part
p. 2505 - 2508
(2009/12/08)
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- SELECTIVE PRODUCTION OF SULPHOXIDES
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The invention pertains to a process for producing a sulphoxide compound, comprising oxidizing a thioether compound with an ozonide formed from a olefin and ozone, to obtain the corresponding sulphoxide compound, provided that the olefin is not ethene. The ozonide converts thio - ether compounds selectively, unlike its art - known oxidizing counterparts. The milder ozonide does not require manipulation of the stoichiometric amount of available oxidizing agent during the reaction, to prevent the formation of sulphones.
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Page/Page column 11
(2009/03/07)
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- Oxidation of sulfides with hydrogen peroxide catalyzed by 10,10′-linked bisflavinium perchlorates
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A series of bisflavinium perchlorates linked with methylene spacer at N10-position exhibit high catalytic activities for the oxidation of sulfides with hydrogen peroxide affording the corresponding sulfoxides. The kinetic studies revealed that the reaction rates are dependent on the spacer length of the catalysts due to their specific intramolecular electrochemical behaviors.
- Imada, Yasushi,Ohno, Takashi,Naota, Takeshi
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p. 937 - 939
(2008/02/04)
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- 2-Iodylphenol ethers: Preparation, X-ray crystal structure, and reactivity of new hypervalent iodine(V) oxidizing reagents
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2-Iodylphenol ethers were prepared by the dimethyldioxirane oxidation of the corresponding 2-iodophenol ethers and isolated as chemically stable, microcrystalline products. Single-crystal X-ray diffraction analysis of 1-iodyl-2-isopropoxybenzene 8c and 1-iodyl-2-butoxybenzene 8d revealed pseudopolymeric arrangements in the solid state formed by intermolecular interactions between IO2 groups of different molecules. 2-Iodylphenol ethers can selectively oxidize sulfides to sulfoxides and alcohols to the respective aldehydes or ketones.
- Koposov, Alexey Y.,Karimov, Rashad R.,Geraskin, Ivan M.,Nemykin, Victor N.,Zhdankin, Viktor V.
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p. 8452 - 8458
(2007/10/03)
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- HIO3 in the presence of wet SiO2: A mild and efficient reagent for selective oxidation of sulfides to sulfoxides under solvent-free conditions
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In the presence of wet SiO2, HIO3 is highly efficient for the selective oxidation of sulfides to sulfoxides. It may be applied to any type of dialkyl and alkyl aryl sulfides. It develops under solvent-free conditions, and gives high yield in the presence of different functional groups on the sulfide at room temperature.
- Lakouraj,Tajbakhsh,Shirini,Tamami, M. V. Asady
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p. 775 - 784
(2007/10/03)
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- Selective oxidation of sulfides to sulfoxides using IBX-esters
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IBX-esters (esters of 2-iodoxybenzoic acid) are convenient hypervalent iodine reagents for the clean and selective oxidation of organic sulfides to sulfoxides. This reaction proceeds without over-oxidation to sulfones and is compatible with the presence of the hydroxy group, double bond, phenol ether, benzylic carbon, and various substituted phenyl rings in the molecule of the substrate.
- Koposov, Alexey Y.,Zhdankin, Viktor V.
-
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- Silica sulfuric acid catalysis the oxidation of organic compounds with sodium bromate
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The oxidation of organic compounds by sodium bromate/silica sulfuric acid under solvent-free conditions and in CH2Cl2 have been studied at room temperature.
- Shaabani, Ahmad,Soleimani, Kamal,Bazgir, Ayoob
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p. 3303 - 3315
(2007/10/03)
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- Cerium(III) bromate as a new reagent in oxidation of organic compounds
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Cerium(III) bromate, prepared by the reaction of barium bromate with cerium(III) sulfate, can be used for the oxidation of alkylarenes, alcohols, and sulfides. Products are obtained in high yields under mild conditions. Ce(BrO3)3 is an unique, dual property reagent in which the anion is the oxidant and the cation a catalyst. Stoichiometric studies indicate that bromate is reduced to bromide under these conditions, making the process highly efficient.
- Shaabani, Ahmad,Lee, Donald G.
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p. 1845 - 1854
(2007/10/03)
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- Efficient and Mild Oxidation of Sulfides to Sulfoxides by Iodosobenzene Catalyzed by Cr(salen) Complex
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Cr(Salen) 1 is found to be an efficient catalyst for the oxidation of various sulfides to sulfoxides with iodosobenzene as terminal oxidant. Both aryl and alkyl sulfides are selectively converted into sulfoxides in excellent yields (>90%).
- Kim, Sung Soo,Rajagopal, Gurusamy
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p. 2461 - 2463
(2007/10/03)
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- Hexamethylenetetramine-bromine complex (HMTAB) on wet silica: Oxidation of alcohols and sulfides
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Secondary or benzylic alcohols and sulfides are converted into their corresponding carbonyl and sulfoxide compounds efficiently using wet silica supported HMTAB complex at room temperature.
- Shaabani, Ahmad,Teimouri, Mohammad Bagher,Bazgir, Ayoob
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p. 1975 - 1977
(2007/10/03)
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- Reactions of chlorine dioxide with organic compounds: Selective oxidation of sulfides to sulfoxides by chlorine dioxide
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A novel method for the selective oxidation of various types of sulfides to sulfoxides using chlorine dioxide as the oxidant is proposed.
- Kutchin,Rubtsova,Loginova
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p. 432 - 435
(2007/10/03)
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