Sharif Digital Repository

The novel unsymmetrical tetradentate Schiff base complexes of Co(II) and Pd(II) with the general formula M(SaI.Phen.Acac.) and M(Sal.Phen. Naph.), have been synthesised by template and non-template method  

Complexes of Ni II-(N,N′-bis(2-hydroxy, 3-methoxy benzaldehyde)-1,2-propandiimine) can be electro-polymerized onto GC electrode in an alkaline solution to give an electro-active film strongly adhered on the electrode surface. In alkaline solution, this poly-(Ni II{sal-1,2-pn(3-OMe) 2})/GC film shows the typical voltammetric response of a surface-immobilized redox couple, as can be anticipated for the Ni 2+/Ni 3+ transitions into the film. In addition, the film exhibits a potent and persistent electro-catalytic activity towards the oxidation of 1- and 2-propanol. In CV studies, in the presence of these alcohols, poly-(Ni II{sal-1,2-pn(3-OMe) 2})/GC electrode shows a new oxidation peak for the... 

Two copper(II)complexes were synthesized through the reaction of Cu(OAc)2·H2O with a Schiff-base ligand (1-(((3,4-dichlorophenyl)imino)methyl)naphthalen-2-ol)and a diazo ligand (1-((3,4-dichlorophenyl)diazenyl)naphthalen-2-ol)in methanol. The complexes and ligands were characterized employing elemental analysis and electronic spectra. In addition, the ligands were fully characterized by using several 1D and 2D NMR techniques. Single crystal X-ray crystallography was also used for the characterization of some of these materials. Due to finding out the effect of Schiff-base and diazo ligands nature on the catalytic activity, the complexes were catalytically compared in one-pot azide-alkyne... 

Tridentate Schiff-base ligands derived from condensation of 3-formyl-4-hydroxybenzyl-triphenylphosphonium chloride with glycine, L-alanine, L-valine, L-leucine and L-phenylalanine in the presence of Zn(OAc)2·2H2O form five new water-soluble Zn(II) complexes, which were characterized by elemental analyses, IR, electronic absorption and 1H, 13C NMR spectroscopies. In the IR spectra of the complexes, the difference between the asymmetric and the symmetric carboxylate stretching frequencies is larger than ∼210 cm-1, which implies that the carboxylate groups are monodentate. UV-Vis electronic absorption studies show that Zn(II) functions as a trap for the Schiff-base intermediate. Schiff-base... 

The electrochemical behavior of methimazole, as an antithyroid agent, is investigated on the surface of a carbon-paste electrode modified with a newly synthesized Schiff base complex of cobalt. The prepared modified electrode showed an efficient catalytic role in the electrochemical oxidation of methimazole, leading to remarkable decrease in oxidation overpotential and enhancement of the kinetics of the electrode reaction. The mechanism of the electrocatalytic process on the surface of the modified electrode is analyzed by obtaining the cyclic voltammograms in various potential sweep rates and pHs of the buffer solutions. The differential pulse voltammetry is applied as a very sensitive... 

New water-soluble zinc(II) Schiff-base complexes derived from amino acids (glycine, L-phenylalanine, and L-valine) 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, electronic, 1H NMR, and 13C NMR spectra. In the IR spectra of the complexes, the large difference between the asymmetric νas(COO) and symmetric νs(COO) carboxylate stretch, Δν(νas(COO)-νs(COO)) of 199-247 cm-1, indicates monodentate coordination of the carboxylate group. Spectral data showed that in these complexes the ligand is a tridentate ONO moiety, coordinating to the metal... 

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 electrochemical oxidation of thiocytosine on the surface of carbon-paste electrode modified with Schiff base (salophen derivatives) complexes of cobalt is studied. The effect of the substituents in the structure of salophen on the catalytic property of the modified electrode is investigated by using cyclic and differential pulse voltammetry. Cobalt (II)-5-nitrosalophen, because of its electrophilic functional groups, leads to a considerable enhancement in the catalytic activity, sensitivity (peak current), and a marked increase in the anodic potential of the modified electrode. The differential pulse voltammetry is applied as a very sensitive method for the detection of thiocytosine. The... 

Two series of the novel unsymmetrical diimino tetradentate Schiff bases derived from phenylenediamine and 1,3-naphthalene diamine and their vanadyl complexes were synthesized by template and non-template methods and characterized by 1H, 13C NMR, IR, UV-Vis and elemental analysis. These complexes are used as catalysts for the selective aerobic oxidation of cyclohexene. The catalytic activity increases as the number of electron-donor groups decreases, and the catalytic selectivity is varied by changing the substituents on the ligands. The catalytic system described here is an efficient and inexpensive method for the oxidation of olefins, with the advantages of high activity, selectivity,... 

Novel vanadyl Schiff base complexes with the general formula VOLx (x = 7-18) were synthesized and characterized by physicochemical methods. Only an orange polymeric form was obtained for VOL13, both brown polymeric and green monomeric forms were obtained for VOLx, x = 16, 17. These observations suggest that in these complexes oxovanadium(IV) exhibit a coordination number of five. Systematic substitution on the ancillary ligand have allowed V(V)/V(IV) reduction potentials to be tuned over a range of approximately 130mV. The complexes are catalysts for the aerobic oxidation of cyclohexene. Catalytic activity increases with increasing V(V)/V(IV) reduction potential and the catalytic selectivity... 

The novel N2O2 unsymmetrical tetradentate Schiff bases complexes are used as catalysts for the selective aerobic oxidation of cyclohexene. In general, conversion percentages decrease with increasing ΔEp and decreasing Eredox 0′. Catalytic activity increases with decrease of the number of electron-donating groups and the catalytic selectivity varies according to the types of substituents in the ligands. The catalytic system described here is an inexpensive method for selective oxidation of olefins, with advantages of high activity, selectivity, re-usability and short reaction times. Analysing GC and redox potential results shows a moderate correlation between selectivity and activity. © 2004... 

In this paper, the interactions of cobalt(III) tetradentate Schiff-base complexes, [Co(S-MeO-salophen)]ClO4, (1), [Co(5-NO 2-salophen)]ClO4, (2), and [Co(5-Br-salophen)]ClO 4, (3), with dopamine, an important neurotransmitter, have been investigated. The formation and kinetic constants for complex formation of [Co(3-MeO-salophen)]ClO4, (1), with dopamine were determined spectrophotometrically in H2O/EtOH solution (4:1) at 30°C by using the Benesi-Hildbrand and Guggenheim equations, respectively. The stoichiometry has been found to be 1:1. The rate and equilibrium constants for the coordination of dopamine to (Co(3-MeO-salophen)]ClO4 were found to be 0.0053 min-1 and 1600 dm3 mol-1,... 

Oxygen evolution was observed upon mixing solid manganese(III) bidentate Schiff base complexes with aqueous solutions of cerium(IV) ammonium nitrate. However, oxygen evolution was not observed upon mixing solutions of the complexes (in acetonitrile) with Ce(IV). Electron-withdrawing substituents on the Schiff base ligands (NO2, Br) enhanced the reactivity of the manganese complexes toward oxygen evolution. Oxygen evolution was also affected by R groups on the ligands, in the order Me > Et Bz. © 2009 Springer Science+Business Media B.V  

Ship-in-a-bottle complex of nickel(II) containing the ligand N,N′-bis(2,4-dihydroxyacetophenone)-2,2-dimethylpropandiimine (H 2{salnptn(4-OH)2}) has been synthesized in zeolite Y. The characteristics of the encapsulated complex are identified by the methods of EDX, SEM, XRD, FT-IR and cyclic voltammetry. A catalytic effect in the electrochemical oxidation of glucose, fructose and sucrose, and a blocking effect in stevioside oxidation are demonstrated on the Ni II{salnptn(4-OH)2}-Y/CPE. The effects of some parameters, such as potential scan rate and concentration of carbohydrates are investigated. The rate constants for the catalytic reaction (k′) of carbohydrates are also obtained. The... 

A targeted new dioxo molybdenum(VI) ONO Schiff base complex was prepared for catalyzing epoxidation of olefins in water. This complex was characterized by FT-IR, NMR, UV–Vis, and X-ray crystallography techniques. DFT calculations are additionally performed to find ground and transition states for finding electronic structure and UV–Vis assignment. Afterward, a new protocol was defined for sustainable catalytic epoxidation of olefin in water using this complex as a green catalyst, and also remarkable results are obtained, such as turn over number up to 1400. © 2020 Elsevier B.V  

The water-soluble cobalt(II) tetradentate Schiff base complex [Co(II)L](ClO4)2, L: (N,N′-bis{5-[(triphenylphosphonium)-methyl]salicylidine}-o-phenylenediamineperchlorate has been synthesized and characterized. This complex forms charge transfer (CT) complexes with imidazole and 1-methylimidazole. The formation constant, molar absorptivity (ε′), and thermodynamic parameters for charge transfer complexes formation of cobalt(II) Schiff base complexes with imidazole derivatives were determined by using UV-vis spectrophotometric method in aqueous solutions at constant ionic strength (I = 0.2 mol dm-3 KNO3) at pH 6.0 and various temperatures between 292 and 315 K. © 2007 Elsevier B.V. All rights... 

The formation constants for 1:1 molecular complex formation between water-soluble cobalt(II) tetradentate Schiff base complex, disodium[{bis(4- methoxy-5-sulfo-salicylaldehyde)-4,5-dimethyl-o-phenylenediiminato}cobalt(II)], Na2[Co(SO3-4-meosal-4,5-dmophen)], and nucleotides, adenosine-5′-triphosphate (ATP) and cytidine-5′-triphosphate (CTP), in mixed solvent systems of ethanol and water with different volume fractions of ethanol and water have been determined spectrophotometrically at constant ionic strength (I = 0.2 mol dm-3 NaClO4) and temperature 278 K. Trends in the values of formation constants according to the volume fractions of ethanol and water in ethanol and water mixed solvent... 

Ni II-(N,N′-bis(2,4-dihydroxyacetophenone)-2, 2-dimethylpropandiimine (Ni II{salnptn(4-OH) 2}) complex has been encapsulated within the supercage of zeolite-NaY by reacting Ni 2+-exchanged NaY with the flexible Schiff-base ligand that diffuses into the cavities. The encapsulated complex is characterized by EDX, scanning electron microscopy, powder X-ray diffraction, FT-IR, and cyclic voltammetry studies. Density functional calculation is being carried out on both the free nickel Schiff-base complex and that encapsulated in NaY zeolite to investigate changes in structural parameters, energies of the HOMO and LUMO, and absolute hardness and softness. Electrochemical properties of the NaY...