Sharif Digital Repository

We present the first density functional theory study on α-ketoglutarate dependent halogenase and focus on the mechanism starting from the iron(IV)-oxo species. The studies show that the high-valent iron(IV)-oxo species reacts with substrates via an initial and rate determining hydrogen abstraction that is characterized by a large kinetic isotope effect (KIE) of 26.7 leading to a radical intermediate. This KIE value is in good agreement with experimental data. The reaction proceeds via two-state reactivity patterns on competing quintet and septet spin state surfaces with close lying hydrogen abstraction barriers. However the septet spin radical intermediate gives very high barriers for... 

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... 

The efficient catalytic systems were investigated for the oxidation of various sulfide by manganese(III)-oxazoline complexes, [Mn(phox)2(MeOH)2]ClO4 and Mn(phox)3 (Hphox = 2-(2′-hydroxyphenyl)oxazoline). These complexes were found efficient catalysts for the oxidation of sulfides with urea hydrogen peroxide (UHP) in short reaction times (5 min) and under mild condition. Sulfoxides were obtained as the main products together with variable amounts of sulfones. The efficiency of the catalytic system was strongly influenced by the nature of solvents and axial ligands so the best yields were achieved in a mixture of methanol: dichloromethane and in the presence of imidazole as co-catalyst. © 2008... 

A new efficient catalytic system was investigated for the epoxidation of various olefins by cis-dioxo-bis[2-(2′-hydroxyphenyl)-oxazolinato]molybdenum(VI), cis-[MoO2(phox)2], and TBHP as oxidizing agent. Using this system as catalyst for the oxidation of aliphatic substrates at 80 °C gives the epoxide as the sole product with yields up to 100% and turnover frequency up to 5000 h-1. The efficiency of the catalyst is strongly influenced by the nature of solvent, reaction time and temperature, and a significant increase in the epoxide yields is observed in higher temperatures and longer reaction times. © 2009 Elsevier B.V  

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  

Combined experimental and theoretical studies on the reactivity of iodosylbenzene (PhIO) show that PhIO is capable of activating weak C-H bonds of hydrocarbons via a hydrogen abstraction mechanism. © 2009 The Royal Society of Chemistry  

The synthesis of a Mo(VI) Schiff base complex, cis-[MoO2{(4,6-bis(tert-butyl)-2-{(benzyl)iminomethyl}phenolate)2}], cis-[MoO2(L)2] where L = 4,6-bis(tert-butyl)-2-{(benzyl)iminomethyl}phenol, derived from benzylamine and 3,5-di-tert-butylsalycilaldehyde is reported. Full characterization of this complex was accomplished with elemental analyses, spectroscopic studies (NMR, IR and electronic) and X-ray structure analysis. This complex was tested as a catalyst for the homogeneous oxidation of olefins. The Mo(VI) complex is catalytically active for the epoxidation of aliphatic substrates at 80 °C, yielding the epoxide as the sole product in yields up to 100% and turnover numbers up to 5000.... 

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. ©... 

Achieving high densification parameter is an essential factor for metal-based composites to represent excellent mechanical characteristics. Among various compaction methods, double-pressing double-sintering (DPDS) has gained the attraction of researchers to fabricate metal-matrix composites (MMCs) as an efficient technique over the last decade. In this process, the powder will be pre-pressed and then pre-sintered; it helps reduce work hardening and prepare the sample for better densification in the next pressing and sintering step. By employing the above-mentioned method, carbon nanotube (CNT) reinforced aluminum nanocomposites; ZrB2 reinforced copper nanocomposites; and CNT reinforced...