Sharif Digital Repository

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  

A mononuclear mixed ligand complex of iron, [FeIII(N-OPh-sal)(acac)EtOH], where Hacac and N-HOPh-Hsal denote acetylacetone and N-hydroxyphenyl-salicylideneamine, respectively, has been synthesized and characterized by elemental analysis, spectral studies and X-ray crystallography. The catalytic system containing this complex and urea hydrogen peroxide as oxidizing agent was used to selectively oxidize a range of sulfides to the corresponding sulfoxides in good yields under mild conditions. The electronic spectra of the catalytic system were applied to explore reactivity and stability of the catalyst during sulfide oxidation reactions and to examine the nature of active species, as well. ©... 

A novel binuclear iron(III)-salicylaldazine complex has been synthesized and characterized by various techniques such as IR and UV–Vis spectroscopy and X-ray crystallography. The catalytic oxidation of sulfides in the presence of the aforementioned complex was explored at room temperature using urea hydrogen peroxide (UHP) as an oxidant. Effects of different reaction conditions consisting catalyst and oxidant amount, solvent effect and reaction time on the catalytic activity and selectivity in the reaction of methylphenylsulfide oxidation has been surveyed. Perfect selectivity toward sulfoxide was achieved after 15 min in CH3CN by choice of a properly optimized reaction condition. © 2020... 

Catalytic studies were performed to develop a simple oxidation system for olefins and sulfides using manganese(III)-tridentate Schiff base complex, Mn(N-OPh-sal)(acac)(EtOH) (N-HOPh-Hsal = N-hydroxyphenyl-salicyldienamine, Hacac = acetylacetone), and urea-hydrogen peroxide (UHP) as terminal oxidant. Conversions up to 90% for olefins at 0 °C and 96% for sulfides at room temperature as well as sulfoxide selectivity up to 73% were achieved in short reaction times. Also this study confirms the accelerating effect of strong π-donor axial ligands such as imidazole (ImH) on the oxidation reactions. © 2008 Elsevier B.V. All rights reserved  

The catalytic activity of two manganese(III)-oxazoline complexes [Mn(phox)2(CH3OH)2]ClO4 and Mn(phox)3 (Hphox = 2-(2′-hydroxylphenyl)oxazoline), was studied in the epoxidation of various olefins. All of epoxidation reactions were carried out in (1:1) mixture of methanol:dichloromethane at room temperature using urea hydrogen peroxide (UHP) as oxidant and imidazole as co-catalyst. The epoxide yields clearly demonstrate the influence of steric and electronic properties of olefins, the catalysts and nitrogenous bases as axial ligand. [Mn(phox)2(CH3OH)2]ClO4 catalyst with low steric properties has higher catalytic activity than Mn(phox)3. The highest epoxide yield (95%) was achieved for indene... 

Novel molybdenum complex, cis-[MoO2(phox)2] has been synthesized and characterized by IR, 1H NMR, elemental analyses (CHN), and X-ray molecular structure determination methods. This complex was found to be an efficient, selective catalyst for the oxidation of various sulfides to sulfoxides with urea hydrogen peroxide (UHP) in excellent yields (100% for diallylsulfide) and short reaction times (20 min) at room temperature. The catalytic system oxidizes diallylsulfide chemoselectively to its corresponding sulfoxide without any over oxidation in double bond. © 2007 Elsevier B.V. All rights reserved  

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... 

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... 

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... 

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...