A mononuclear copper(II) complex of a protonated unsymmetrical dinucleating Schiff base ligand

Reaction of the unsymmetrical and potentially dinucleating Schiff base ligand HL¹ with copper(II) salts has given mono- and dinuclear metal complexes. The structure of a mononuclear complex of diprotonated HL¹, [Cu(H₂L¹)(OH₂)](ClO₄)₃·H₂O·CH₃OH_, has been determined.     

Host (nanocavity of zeolite-Y)/guest (Mn(II), Co(II), Ni(II) and Cu(II) complexes of pentadendate Schiff-base ligand) nanocomposite materials (HGNM): application in the heterogeneous oxidation of cyclohexene

Transition metal (M = Mn(II), Co(II), Ni(II) and Cu(II)) complexes with pentadendate Schiff-base ligand; N,N′-bis(salicylidene)-2,6-pyridinediaminato, H₂ [sal-2,6-py]; was entrapped in the nanocavity of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of bis(salicylaldiminato)metal(II); [M(sal)₂]-NaY; in the supercages of the zeolite, and (ii) in situ Schiff condensation of the metal(II) precursor complex with the corresponding 2,6-pyridinediamine; [M(sal-2,6-py)]-NaY. The new materials were characterised by several techniques: chemical analysis, spectroscopic methods (DRS, BET, FTIR and UV/Vis), conductometric and magnetic measurements. Analysis of the data indicates that the M(II) complexes are encapsulated in the nanodimensional pores of zeolite-Y and exhibit different from those of the free complexes, which can arise from distortions caused by steric effects due to the presence of sodium cations, or from interactions with the zeolite matrix. The Host–Guest Nanocomposite Materials (HGNM); [M(sal-2,6-py)]-NaY; catalyzes the oxidation of cyclohexene with tert-butylhydroperoxide (TBHP). Oxidation of cyclohexene with HGNM gave 2-cyclohexene-1-one, 2-cyclohexene-1-ol and 1-(tert-butylperoxy)-2-cyclohexene. [Mn(sal-2,6-py)]-NaY shows significantly higher catalytic activity than other catalysts.     

Synthesis and characterization of palladium (II) complex of Schiff base ligand: CS bond cleavage and catalytic activity

Reaction of ligand, L-CH₂Ph with Pd(CH₃CN)₂Cl₂ in acetonitrile in presence of PPh₃ and subsequent addition of NaClO₄ yielded Pd(II) complex, [Pd(L)(PPh₃)](ClO₄) 1 due to the SC (CH₂Ph) bond cleavage during complexation. Complex 1 was characterized by spectral analysis and the structure was authenticated by single crystal X-ray diffraction. The diffraction analysis revealed that the monoanionic ligand binds with palladium (II) in (N, N, S) fashion in a distorted square planar geometry where the fourth position is occupied by one tri phenyl phosphine group. One ClO₄⁻ ion satisfies the charge of the former aggregate, [Pd(L)(PPh₃)]⁺. The complex [Pd(L)(PPh₃)](ClO₄), 1 exhibits a very good catalytic activity towards CC bond formation.     

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

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, together with variable amounts of sulfones (?9%), depending on the nature of the substrate.     

Studies on the oxidation of phenols catalyzed by a copper(II)–Schiff base complex in aqueous solution under mild conditions

The catalytic oxidation of phenol with hydrogen peroxide using a synthetic copper(II)–Schiff base complex as catalyst has been investigated in phosphate buffer at pH 7 and 25 °C. In order to further investigate the reaction pathway, the catalytic oxidation of hydroquinone, p‐benzoquinone and catechol were also studied under the same conditions. These reactions were found to be pseudo‐first‐order with respect to the concentration of phenolic substances. The rate constants were also calculated. In the presence of catalyst, the kinetics and the HPLC analysis showed that for the first step phenol was oxidized to hydroquinone and catechol, and the catalyst easily promoted the formation of hydroquinone but not catechol, for the second step the dihydroxybenzenes were further oxidized to benzoquinone, and lastly short‐chain acids, including maleic acid and oxalic acid, were formed. The activity of the catalyst hardly decreased during the whole reaction. Addition of imidazole accelerated the oxidation of phenol. The catalytic decomposition of hydrogen peroxide using this catalyst was also investigated. Copyright © 2005 Society of Chemical Industry     

Dinuclear based polymeric copper(II) complexes derived from a Schiff base ligand: effect of secondary bridging moieties on geometrical orientations and magnetic properties

[1 + 1] condensation of salicylaldehyde and 2-aminobenzenesulfonic acid led to the formation of the acyclic Schiff base o-[(o-hydroxyphenyl)methylideneamino]benzenesulfonic acid (H₂L) which, upon reaction with Cu(II) salts in the presence of triethylamine or 4,4′-bipyridine, formed a 2D polymeric species [Cu₂L₂]_n (1) via sulfonate bridge and a 1D polymeric complex [{Cu₂L₂(4,4′-bipy)}·DMF]_n (2) via 4,4′-bipyridine bridge, respectively. The copper cations sit on O₄N basal- or O₃N₂ facial-edge-sharing inverted square pyramidal environments in 1 or 2, respectively. In spite of their comparable compositions, the relative orientations of the metal polyhedra affect the magnetic properties of these polymers since 1, in contrast to 2, presents a strong exchange interaction of an antiferromagnetic nature.     

Structure and magnetic properties of A Cu(II) coordination polymer supported by a tetrapodal Schiff base ligand

A Cu(II) Schiff base coordination polymer, {[Cu₃L(μ₂-NO₃)₂·(H₂O)₂].3H₂O}_n, is readily prepared by complexation of the tetrapodal Schiff base, H₄L (H₄L = 1,1,1,1-tetrakis[(salicylaldimino)methyl]methane), with cupric nitrate trihydrate. It has been demonstrated that the coordination polymer consists of linear trinuclear Cu(II) entities, and displays a cooperative coordination mode for nitrate anions, coordinated water molecules, and Schiff base ligands to Cu(II) ions. In addition, variable-temperature magnetic susceptibility measurements reveal a strong antiferromagnetic coupling interaction between adjacent copper(II) ions with large J value of − 289.66 cm^− 1.     

An evaluation of the application of a TiO2/ Cu(II)/solar simulated radiation system for selective oxidation of benzyl alcohol derivatives

BACKGROUND: The conversion of hydroxybenzyl alcohols, nitro‐benzyl alcohol and methoxybenzyl alcohols into the corresponding aldehydes is attempted in aqueous solution by Cu(II) (which reduces to Cu(0)), at room temperature, under acidic and deaerated conditions, using TiO₂ solar simulated light photocatalysis. RESULTS: Under the experimental conditions adopted, the yields of the corresponding hydroxyaldehydes, when Cu(II) was completely reduced to Cu(0), were 21.6% for 4‐hydroxybenzaldehyde, 11.5% for 3‐hydroxybenzaldehyde and 20.2% for 2‐hydroxybenzaldehyde. Higher conversions of 2‐methoxybenzyl alcohol and 4‐methoxybenzyl alcohol were recorded relative to unsubstituted benzyl alcohol. A selectivity of 5.2%, at 50% conversion of the substrate, was observed for the oxidation of 4‐nitrobenzyl alcohol to 4‐nitrobenzaldehyde. For high degrees of aromatic alcohols conversion, oxidation of the generated aldehydes to the corresponding benzoic acid derivatives is observed. CONCLUSION: The introduction of substituents into the aromatic alcohols structure changes the photocatalytic oxidation rate and product selectivities with respect to that previously observed for unsubstituted benzyl alcohol. In particular, the presence of both electron donating (hydroxy, methoxy groups) and electron withdrawing (nitrogroup) groups on the aromatic ring of the substrate causes a detrimental effect on the selectivity of the process with respect to the case of benzyl alcohol. © 2012 Society of Chemical Industry     

Synthesis,X-ray structure and study of a mixed ligand iron(III) complex with tridentate Schiff base as a homogeneous catalyst in the efficient oxidation of sulfides

A mononuclear mixed ligand complex of iron, [Fe^III(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.     

Performance investigation of Fe3O4 blended poly (vinylidene fluoride) membrane on filtration and benzyl alcohol oxidation: Evaluation of sufficiency for catalytic reactors

Fe_3O_4-PVDF membranes were prepared by blending of magnetic Fe_3O_4 powders with polyvinylidene fluoride to investigate whether those were usable or not in catalytic membrane reactors. Filtration performances and catalytic activity of membranes in microwave conditions were measured in separate processes. Composite Fe_3O_4-PVDF membranes were characterized by TG-DTA, FTIR, XRD, SEM and contact angle techniques.Disappearing of α-phases at PVDF was observed with increasing amount of additives from XRD diffraction patterns. Decomposition of polymer fastened due to catalytic effect of Fe_3O_4. Finger-like structures and large number of small pores were observed at the SEM images. Those provided effective transportation of substrate among the active sites of catalyst. At the experiments conducted in batch reactor, 51%, 77%, 66% and 63% benzyl alcohol conversion were recorded for 2%, 4%, 6% and 8% Fe_3O_4-PVDF composite pieces respectively. Catalyst were separated magnetically and reused several times. On the other hand Fe_3O_4 blended PVDF membranes provided improved flux and BSA rejection compared with performance of bare PVDF membrane; 41.6% BSA rejection was obtained with 4% Fe_3O_4-PVDF whereas it was only 6.7% for PVDF. Fe_3O_4-PVDF composites performed high activity for the benzyl alcohol oxidation in batch reactor and also better filtration at filtration cell. These results promise to obtain practical and low cost membrane material for catalytic reactors usable in microwave support to get fast results.     

Highly salicylate-selective membrane electrode based on a new thiomacrocyclic Schiff base complex of binuclear copper(II) as neutral carrier

New binuclear metallic complexes of thiomacrocyclic Schiff base, 3,9,13,19 -tetraphenyl-6,16-dithione-1,11-dithio-4,5,7,8,14,15,17,18-octaazacycloeicosa-3,8,13,18-tetraene binuclear metal(II) [M(II)₂-TDDOCT] (M = Cu, Co, Ni), were synthesized and their anion response characteristics were investigated. The performances of the electrodes are considerably influenced by the nature of the central metals. The Cu(II) complex-based electrode exhibited a good selectivity to salicylate anion with an anti-Hofmeister selectivity pattern: Sal⁻ > ClO₄⁻ > SCN⁻ > I⁻ > Benzoate > B_r⁻ > Acetate > F⁻ > SO₃²⁻ > NO₂⁻ > Cl⁻ > NO₃⁻ > SO₄²⁻ > H₂PO₄⁻. The electrode had an excellent linear response to Sal⁻ from 9.0 × 10^− 7 to 1.0 × 10^− 1 M with a slope of − 59.3 mV per decade,a detection limit of 5.0 × 10^− 7 M, and a fast response time within 15 s over the entire concentration series in phosphate buffer solutions of pH 5.0 at 25 °C. Spectroscopic techniques and the influence of lipophilic charged additives on the electrode behavior were used to investigate the response mechanism to Sal⁻. The electrode can be applied to the direct determination of salicylate in human urine and pharmaceutical samples and the results obtained are in accord with the results from a standard method.     

Preparation and characterization of reinforced poly(vinyl alcohol) films by a nanostructured,chiral, L-leucine based poly(amide-imide)/ZrO2 nanocomposite through a green method

In the present investigation, at first, the surface of ZrO₂ nanoparticles was modified with a bioactive and biocompatible diacid based on leucine amino acid as a coupling agent. The grafting of diacid on the surface of ZrO₂ was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Then, the synthesis of poly(amide-imide)/ZrO₂ nanocomposite (PAI/ZrO₂ NC) was performed through ultrasonic technique. The obtained NCs demonstrated good thermal stability. Field emission scanning electron microscopy and transmission electron microscopy analysis showed that the average diameter of NP was around 15–20 nm. Finally, the resulting NC, was used as a nano-filler and was incorporated into the poly(vinyl alcohol) (PVA) in order to improve its mechanical and thermal properties. The PVA/PAI–ZrO₂ NC films were characterized by different techniques. The data indicated that the thermal and mechanical properties of the PVA/PAI–ZrO₂ NC were enhanced. It was attributed to the good dispersion of filler into the PVA matrix as a result of hydrogen bonding.     

Oxovanadium(IV) salicylidene Schiff base complex anchored on mesoporous silica MCM-41 as hybrid materials: a robust catalyst for the oxidation of sulfides

Oxovanadium(IV) Schiff base complex have been anchored onto the surface of purely siliceous MCM-41 and tested for its activity as catalyst for the oxidation of sulfides. This catalyst could alter this oxidation reaction extremity, exhibiting excellent yields with 100 % selectivity. The intercalation of the complex inside the silica matrix was supported by various characterization techniques like X-ray diffraction, differential thermogravimetric (TG-DTA), BET measurements, UV–Vis diffuse reflectance spectroscopy and Fourier transform infrared spectroscopy (FT-IR). The stability of the catalyst during the course of the reaction was confirmed from its post catalytic FT-IR and XRD analysis. The catalyst could be reused five times without notable loss of its catalytic activity and efficiency which indicates that the metal-Schiff base moiety is intact and the coordination environments are not altered during the reaction.     

2,2,6,6-Tetramethyl piperidine-1-oxyl (TEMPO)-mediated catalytic oxidation of benzyl alcohol in acetonitrile and ionic liquid 1-butyl-3-methyl-imidazolium hexafluorophosphate [BMIm][PF6]: Kinetic analysis

TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyl) is electrochemically oxidized to a stable form of the cation (TEMPO⁺) in acetonitrile (CH₃CN) or 1-butyl-3-methyl-imidazolium hexafluorophosphate ([BMIm][PF₆]) media. Cyclic voltammograms were characterized by a well-defined one-electron reversible redox couple in both media at low scan rates. The reduced form of TEMPO⁺ is catalytically regenerated in a follow-up chemical reaction with benzyl alcohol (BA) in the presence of 2,6-lutidine. It was observed that in [BMIm][PF₆], the redox currents are largely suppressed compared to that in CH₃CN. The apparent heterogeneous electron-transfer rate constant () of the quasi-reversible redox reaction of TEMPO was determined at a Pt electrode and found to be 1.9 × 10⁻³ cm s⁻¹ and 4.5 × 10⁻² cm s⁻¹ in [BMIm][PF₆] and CH₃CN, respectively. With the aid of chronoamperometry (CA), the homogeneous rate constant for the catalytic oxidation of benzyl alcohol by TEMPO, in the presence of 2,6-lutidine in CH₃CN was estimated to be 5.53 × 10¹ M⁻¹ s⁻¹ which is approximately double, relative to the value of 2.91 × 10¹ M⁻¹ s⁻¹ determined in [BMIm][PF₆].     

Synthesis of a novel chiral Schiff base of (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanonanthracene and its application as ligand in Ti(IV) complex catalyzed asymmetric silylcyanation of aldehydes

A novel chiral salen ligand (R,R)-2 was synthesized through the condensation of (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthracene and 3,5-di-tert-butylsalicylaldehyde. The (salen)Ti(IV) complex formed in situ upon the treatment of ligand 2 and Ti(OPr-i)₄ was proved to be an efficient catalyst for the asymmetric trimethylsilylcyanation of aldehydes. The corresponding cyanohydrins were obtained in high yields (75–97%) with moderate to good enantioselectivities (48–76%).     

Syntheses and characterization of a chelating resin containing ONNO donor quadridentate Schiff base and its coordination complexes with copper(II), nickel(II), cobalt(II), iron(III), zinc(II), cadmium(II), molybdenum(VI) and uranium(VI),

A new mixed Schiff base N,N′-ethylenemono(3-carboxysalicylideneimine)mono(salicylideneimine) has been synthesized by the condensation of equimolar quantities of ethylenediamine, salicylaldehyde and 3-formylsalicylic acid. A polymer supported Schiff base (PS–CH₂–LH₂) has been synthesized by the reaction of chloromethylated polystyrene (containing 3.9 mmol of chlorine per g of resin and 2% cross-linked with divinylbenzene) and the Schiff base N,N′-ethylenemono(3-carboxysalicylideneimine)mono(salicylideneimine). The polymer-anchored Schiff base reacts with metal salt/metal complex and forms polymer-anchored complexes having the formulae PS–CH₂–LCu, PS–CH₂–LNi, PS–CH₂–LCo, PS–CH₂–LFeCl·DMF, PS–CH₂–LZn, PS–CH₂–LCd, PS–CH₂–LMoO₂ and PS–CH₂–LUO₂. The polymer-anchored complexes have been characterized on the basis of elemental analysis, infrared and electronic spectra and magnetic susceptibility measurements. The shifts of the ν(CN) (azomethine) stretch to lower energy and ν(CO) (carboxylic) to higher energy in the polymer-anchored complexes indicate the ONNO donor behaviour of the chelating resin. The metal ions in the metal bound polymers can be leached by hot dilute formic acid, acetic acid or hydrochloric acid. The coordinated dimethylformamide is completely lost on heating the complexes in air. The complexes PS–CH₂–LCu and PS–CH₂–LCo are paramagnetic with square planar structure, PS–CH₂–LNi is diamagnetic with square planar structure and PS–CH₂–LFeCl·DMF is paramagnetic and octahedral, PS–CH₂–LZn and PS–CH₂–LCd are diamagnetic and tetrahedral, PS–CH₂–LMoO₂ and PS–CH₂–LUO₂ are diamagnetic and have octahedral structure. The stoichiometry and the structure of the metal bound polymers are comparable with those of metal complexes of N,N′-ethylenebis(salicylideneimine). This is the first report of the syntheses of a mixed Schiff base and its coordination complexes.