Α-benzoin Oxime Research Articles

The corrosion inhibition performance and mechanism of α-benzoin oxime on copper: A comprehensive study of experiments and DFT calculations

Copper corrosion poses a significant challenge to process stability and chip quality in the field of integrated circuit manufacturing. This study comprehensively explored the corrosion inhibition performance of α-benzoin oxime (bzoxH2) on copper, by employing a combination of experimental methods and computational chemistry. First, after the addition of 0.1 mM bzoxH2, the static etching rate and surface roughness of copper were decreased to 7 Å·min−1 and 1.36 nm, respectively, which indicated that bzoxH2 could reduce the corrosion rate of copper and improve its surface quality. Subsequently, electrochemical behavior analysis showed that the addition of 0.1 mM bzoxH2 resulted in an increase in open circuit potential to 0.185 V, a decrease in corrosion current density to 2.33 µA·cm−2, an increase in polarization resistance to 10589 Ω·cm2, and a high corrosion inhibition efficiency of 96.88 %, suggesting that bzoxH2 significantly enhances the corrosion resistance of copper. Furthermore, studies based on adsorption isotherm models indicated that the adsorption behavior of bzoxH2 on the copper surface formed a dense passivation film through the combination of physical and chemical adsorption mechanisms. This effectively enhanced the corrosion resistance of copper and provided robust protection against corrosion. Finally, the use of X-ray photoelectron spectroscopy technology, along with an in-depth exploration of the geometric structure and chemical reactivity of the bzoxH2 molecule, revealed its complex interaction with specific active sites on the copper surface. These findings provided valuable theoretical insights, along with practical guidance for the development of metal corrosion inhibitors.

Synthesis, Characterization and Biological Activity of Some Mixed Ligand Transitionmetal Complexes

The Schiff bases derived from Salicylaldehyde with substituted amines and alpha benzoin oxime as a primary ligand are prepared by mixed with Cobalt (II), Nickel(II) and Copper (II). Structure have been proposed from elemental examination, like IR, NMR, thermal examination and magnetic susceptibility, Spectroscopic studies suggests that coordination occurs through azomethine nitrogen, hydroxyl group and oxime of the ligand to the metal ions. Elemental analysis of Schiff bases, alpha benzoin oxime and metal complexes are confirmed to stoichiometry of the type ML1L2 where Metals are Cobalt (II) andNickel (II) L1 are Schiff bases and L2 are alpha benzoin oxime. The mixed ligand Co(II) complexes were synthesize by using α-benzoin oxime as a primary ligand and Schiff base prepared from salicylaldehyde and chloroanilines with hydroxyanilines as a secondary ligand. The metal complexes have been characterized different elemental analyses and various chemical techniques such as molar conductance, magnetic susceptibility, infrared, NMR, spectral studies and thermal analysis. The elemental analysis data is consistent with their general formulation as mixed ligand complexes MLL’.xH2O. The bondings and structures of the complexes are discussed in detail on the basis of the results of various chemical studies. All of these metal complexes and ligands have been screened for their biological activities against selected pathogenic microbial strains. The Ditch Plate Method has been used to study the antibacterial activity against E. coli, S. typhi, S. aureusandS. pyogenes.

Deep Eutectic Solvent-Based Microextraction of Lead(II) Traces from Water and Aqueous Extracts before FAAS Measurements.

Microextraction procedures for the separation of Pb(II) from water and food samples extracts were developed. A deep eutectic solvent composed of α-benzoin oxime and iron(III) chloride dissolved in phenol was applied as a phase separator support. In addition, this deep eutectic mixture worked as an efficient extractor of Pb(II). The developed microextraction process showed a high ability to tolerate the common coexisting ions in the real samples. The optimum conditions for quantitative recoveries of Pb(II) from aqueous extracts were at pH 2.0, conducted by adding 150 µL from the deep eutectic solvent. The quantitative recoveries were obtained with various initial sample volumes up to 30 mL. Limits of detection and limits of quantification of 0.008 and 0.025 µg L−1 were achieved with a relative standard deviation (RSD%) of 2.9, which indicates the accuracy and sensitivity of the developed procedure. Recoveries from the reference materials, including TMDA 64.2, TMDA 53.3, and NCSDC-73349, were 100%, 97%, and 102%, respectively. Real samples, such as tap, lake, and river water, as well as food samples, including salted peanuts, chickpeas, roasted yellow corn, pistachios, and almonds, were successfully applied for Pb(II) analysis by atomic absorption spectroscopy (AAS) after applying the developed deep eutectic solvent-based microextraction procedures.

Recyclable Cu(II)-(MAA-EGDMA) catalyst for selective oxidation of alcohols to aldehydes using sodium hypochlorite

Copper(II) α-benzoin oxime complex was synthesized by the reaction between copper(II) benzoate and α-benzoin oxime. The poly methacrylic acid-ethylene glycol dimethacrylate (MAA-EGDMA) was applied as support of copper complex catalyst for oxidation of alcohols to aldehydes using NaClO. The structure and morphology of immobilized Cu(II)-benzoin oxime have been studied by using different analysis including Fourier Transform Infrared (FT-IR) spectroscopy, Scanning Electron Microscopy (SEM) and Thermal Gravimetric Analysis (TGA). The yield of aldehydes was determined by Gas Chromatography (GC) analysis. The immobilized Cu(II)-benzoin oxime indicated a high catalytic activity compared to its absence for the alcohol oxidation with sodium hypochlorite. The effect of the reaction time and temperature, the solvent type, the amounts of catalyst and NaClO were optimized to obtain maximum yield. The prepared catalyst had various benefits such as being inexpensive, environmentally friendly manner, recyclable, reducing the reaction time and increasing the yield. A reaction mechanism is proposed for oxidation of alcohols in the presence of the catalyst.

Cu(II)-Catalyzed C-N Coupling of (Hetero)aryl Halides and N-Nucleophiles Promoted by α-Benzoin Oxime.

We first reported the new application of a translate metal chelating ligand α-benzoin oxime for improving Cu-catalyzed C-N coupling reactions. The system could catalyse coupling reactions of (hetero)aryl halides with a wide of nucleophiles (e.g., azoles, piperidine, pyrrolidine and amino acids) in moderate to excellent yields. The protocol allows rapid access to the most common scaffolds found in FDA-approved pharmaceuticals.

Cu2O-CuO ball like/multiwalled carbon nanotube hybrid for fast and effective ultrasound-assisted solid phase extraction of uranium at ultra-trace level prior to ICP-MS detection

Multiwalled carbon nanotube/Cu2O-CuO ball like hybrid material (MWCNTs/Cu2O-CuO) synthesized using of a green hydrothermal process was evaluated as a new sorbent for solid phase extraction of uranium with inductively coupled plasma mass spectrometry (ICP-MS). According to our best knowledge, this new material was synthesized and used as solid phase extraction adsorbent for the first time in the literature. The characterization of new hybrid material was carried out using Raman spectroscopy, X-ray diffraction (XRD) and scanning electronic microscopy techniques (SEM, SEM-EDX and SEM-Mapping). The characterization results demonstrated that the new hybrid nanostructure was successfully obtained. The ultrasound-assisted solid phase extraction (UA-SPE) procedure was performed using 100 mg of new hybrid sorbent, 1000 μL of a 0.1% (w/v) solution of α-benzoin oxime and 2000 μL of phosphate buffer at pH 7.0 for separation and preconcentration of uranium. Uranium was eluted with 2 M HCl and the levels of uranium was measured by using ICP-MS. The linearity was observed between 2.5 and 100 ng mL−1 concentration range with a good correlation coefficient (r = 0.999, n = 7). The obtained limit of detection and quantitation values were 0.52 and 1.70 ng mL−1, respectively. Under optimum conditions, the preconcentration factor (PF) was calculated as 13.3. The accuracy of the developed method was assessed by analyzing of TMDA-62.2, TMDA-70.2 (Environment Canada) and GBW-07423 certified reference water and soil materials. The proposed UA-SPE-ICP-MS procedure developed with MWCNTs/Cu2O-CuO hybrid material was successfully applied to the analysis of uranium at ultra-traces levels in environmental water and geological rock samples.

Coprecipitation procedure for speciation of chromium in some dairy food product and water samples by FAAS

A new method based on the coprecipitation procedure (CP) for separation/speciation using flame atomic absorption spectrometric (FAAS) determination was proposed for the determination of Cr(III)/ Cr(VI) in some real samples with Co(II)/α-Benzoin oxime precipitate.

Solid phase extraction of Cd, Pb, Ni, Cu, and Zn in environmental samples on multiwalled carbon nanotubes.

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO3 in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L(-1), respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.

A coprecipitation procedure for the determination of some metals in food and environmental samples by flame atomic absorption spectroscopy

A novel, rapid, and simple preconcentration procedure based on the coprecipitation of Cr(III), Cu(II), Fe(III), Pb(II), Pd(II) and Zn(II) ions with Ni(II)–α-benzoin oxime precipitate was developed prior to flame atomic absorption spectrometric determination. The optimum values of the important analytical parameters influencing the quantitative coprecipitation of the analytes were as follows: pH 8.5, amount of α-benzoin oxime: 100 mg, amount of Ni(II) as carrier element: 0.25 mg, time duration: 10 min. The effects of alkali (4000–15 000 mg L−1) and alkaline earth (1000–4000 mg L−1) metals on the recovery were also studied. The alkali metal ions (K+ up to 4000 and Na+ up to 15 000 mg L−1) and alkaline earth metal ions (Mg2+ up to 1000 and Ca2+ up to 4000 mg L−1) did not show any interference effect on the recovery of the analytes. Under the optimized conditions, the detection limits (3s, N = 10) for the analytes were in the range of 0.1–5.3 μg L−1. The accuracy of the presented coprecipitation method was checked by the analysis of certified reference materials. The method was applied to the determination of the analytes in real samples such as natural water and food samples, and good results were obtained (relative standard deviation 95%).

Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by α-benzoin oxime modified Amberlite XAD-2000 resin

A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with α-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48 μg L −1, respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.

Initial employment of α-benzoin oxime as a route to high-nuclearity metal clusters: decanuclear CuII complexes with a wheel topology

The initial employment of alpha-benzoin oxime (bzoxH2) in metal cluster chemistry has provided access to a new family of decanuclear CuII complexes with a loop or single-strand wheel topology; the CuII10 clusters are antiferromagnetically-coupled with an S=0 spin ground state, as expected for even-membered loop arrays of CuII atoms.

Separation of palladium from high level liquid waste of PUREX origin by solvent extraction and precipitation methods using oximes

Separation of palladium from high level liquid waste (HLLW) solution originated from the reprocessing of spent fuel by PUREX process is carried out by solvent extraction and precipitation methods using oximes. In solvent extraction, palladium is extracted from the waste using 1.1×10 −2M α-benzoin oxime in Solvesso 100 as extractant. The loaded organic phase is scrubbed with water prior to the stripping of palladium using the strippants 0.05 M thiourea in 0.1 M HNO 3 and 4 M NH 4OH separately. The recovery of the method is found to be >99.5%. The method has been used to recover Pd in sub mg quantities from actual waste solution originated from the reprocessing of spent fuel from pressurised heavy water reactor (PHWR-HLLW). Studies are also carried out for the separation of palladium using an aqueous solution of sodium salt of dimethyl glyoxime (0.1% w/v) as precipitant. Various parameters which influence the precipitation of palladium such as concentration of the precipitant, concentration of nitric acid in the feed and the behaviour of uranium, plutonium and other fission products at the concentration level encountered in the waste are studied in detail. Under the optimized precipitation conditions separation of Pd is carried out from a synthetic PHWR-HLLW and the recovery is found to be >99.9%. The palladium product obtained from both the methods show high decontamination factors with respect to other fission products and constituents of the waste. Based on these results a scheme has been proposed for the recovery of palladium from HLLW.

SP70-α-benzoin oxime chelating resin for preconcentration–separation of Pb(II), Cd(II), Co(II) and Cr(III) in environmental samples

In the presented work, α-benzoin oxime immobilized SP70 chelating resin was synthesized for separation and preconcentration of Pb(II), Cd(II), Co(II) and Cr(III). The optimization procedure for analytical parameters including pH, eluent type, flow rate, etc. was examined in order to gain quantitative recoveries of analyte ions. The effects of foreign ions on the recoveries of studied metal ions were also investigated. The detection limits (3σ) were found to be 16.0, 4.2, 1.3, 2.4 μg L −1 for Pb, Cd, Co and Cr, respectively. The preconcentration factor was 75 for Pb, 100 for Cd, Co and Cr. The optimized method was validated with certified reference materials and successfully applied to the waters, crops and pharmaceutical samples with good results (recoveries greater than 95%, R.S.D. lower than 10%).

Homogeneous liquid–liquid extraction method for the selective separation and preconcentration of ultra trace molybdenum

A new simple and efficient homogeneous liquid–liquid extraction method for the selective separation and preconcentration of molybdenyl ions was developed. α-Benzoin oxime (ABO) was investigated as a complexing ligand, and perfluorooctanoate ion (PFOA −) was applied as a phase-separator agent under strongly acidic conditions. Under the optimal conditions ([ABO] = 2.1 × 10 −3 M, [PFOA −] = 1.8 × 10 −2 M, [HNO 3] = 1.7 M, [acetone] = 11.8% (v/v)), 10 μg of molybdenum in 5 ml aqueous phase could be extracted quantitatively into 40 μl of the sedimented phase. The maximum concentration factor was 125-fold. Thiocyanate was applied as a chromogenic reagent for the direct spectrophotometric determination of molybdenum in the sedimented phase. The reproducibility of the proposed method is at the most 2.4%. The influence of the type and concentration of acid solution, the concentration of ABO, the type and volume of the water-miscible organic solvent, the concentration of PFOA −, and the effect of different diverse ions on the extraction and determination of molybdenum(VI) were investigated. The proposed method was applied to the extraction and determination of molybdenum(VI) in natural water, Spinach, and Lucerne samples. A satisfactory agreement exists between the results obtained by the proposed method and those reported by GF-AAS.

SYNTHESIS AND CHARACTERISATION OF COMPLEXES OF URANIUM(VI) WITH ACETONE OXIME AND α-BENZOIN OXIME

ABSTRACT In this communication, we report the synthesis and characterization of two uranium(VI) complexes with acetone oxime (HL1) and α-benzoin oxime (H2L2). These complexes have been characterized on the basis of elemental analyses, infrared, UV-Visible absorption and 1H NMR spectra. The reaction of acetone oxime, CH3(C˭NOH)CH3, with U(VI) leads to the formation of a monomeric coordination complex of the formula UO2(H2O)2(L1)2 (1), whereas reaction of α-benzoin oxime, C6H5(C˭NOH)(CHOH)C6H5, with U(VI) leads to the formation of a dimeric coordination complex of the formula [U2O4(OH)2(L3)(HL4)]·H2O (2) where L3=(C6H5)C(O−)˭C(N˭O)(C6H5) and HL4=(C6H5)CH(O−)CH(NHOH)(C6H5) are two new deprotonated ligands derived from H2L2.

SYNTHESIS AND CHARACTERIZATION OF MONONUCLEAR AND BINUCLEAR CHROMIUM(III) COMPLEXES OF α-BENZOIN OXIME

ABSTRACT Irradiation of a THF solution containing Cr(CO)6 and α-benzoin oxime (H2BNO) under various atmospheric conditions, of either argon or vacuum, gave two dichromium(III) complexes of the formulae [Cr(μ-OH)(BNIM)(HBNO)]2 (1) and [Cr(BNIM)(HBNO)(THF)]2O (2) where BNIM is the α-benzoin imine radical anion formed as a result of homolytic cleavage of the oxime N-OH bond. When a related reaction of α-benzoin oxime was carried out with Cr(NO)3 in open atmosphere, Cr(HBNO)3 (3) was obtained. Variable-temperature magnetic susceptibility measurements show a magnetic moment of 8.12 B.M. for the μ-dihydroxo complex (1) at room temperature. This high magnetic moment value strongly confirms the formulation of a dimer consisting of two benzoin imine radicals (S=1/2 coordinated to bridged dichromium(III)(S=3/2) ions. In contrast, the μ-oxo complex (2) shows a magnetic moment of 3.10 B.M. which is even smaller than that observed for the monomeric complex Cr(HBNO)3 (3) at room temperature. Moreover, IR spectral analysis was very informative in assigning the vibrations due to Cr2(OH)2 4+ and Cr2O4+ moieties for the complexes (1) and (2), respectively. Thermal gravimetric analysis (TGA) of complex (2) has shown decompositions due to coordinated THF molecules, followed by gradual decomposition of bezoin imine ligands. Interestingly, a low-energy transition in the Vis-near-IR region assigned as BNIM→Cr(III)LMCT transition was observed for the [Cr(BNIM)(HBNO)(THF)]2O complex.

REACTIVITY OF α-BENZOIN OXIME WITH TUNGSTEN(VI)

In this work, we are presenting various aspects of the reactivity of α-benzoin oxime with tungsten(VI) by altering the pH of the aqueous tungsten salt solution and the ligand/metal ratio. The reactivity of an ethanolic solution of α-benzoin oxime with an aqueous solution of a tungsten salt in the VI oxidation state was investigated at two pH values (1 and 2.5) and various values of the ligand/metal ratio. Based on the experimental conditions, the reaction of α-benzoin oxime (H2L1) with tungsten(VI) leads to the formation of various complexes: (1) a white monomeric coordination complex of the formula [WO2(HL1)2].H2O; (2) a white dimeric coordination complex of the formula [W2O5(H2L1)2(HL1)2] in which HL1 is the deprotonated form of α-benzoin oxime, C6H5(C=NO−)(CHOH)C6H5; (3) a white dimeric coordination complex of the formula [W2O5(L3)2(HL3)2] in which HL3 is the hydrolyzed form, C6H5(C=O)(CHOH)-C6H5, of α-benzoin oxime.

SYNTHESIS AND CHARACTERIZATION OF SOME ORGANOTIN(IV) COMPLEXES OF α-BENZOIN OXIME

Some di- and triorganotin(IV) complexes of α-benzoin oxime of the general formulae R3SnL, R2SnCl2−n L n , and R2SnL have been synthesized by the reactions of the corresponding di- and triorganotin(IV) chlorides with the sodium salt of α-benzoin oxime in the desired molar ratios. All of the compounds have been characterized by elemental analyses and spectral (IR,1H, 13C, and 119Sn NMR) studies.

Reactivity of α-Benzoin Oxime with Molybdenum(VI)

In this work, we have presented various aspects of the reactivity of α-benzoin oxime with molybdenum(VI) based on the pH of the aqueous metal ion solution and the ligand/metal ratio. The reactivity of an ethanolic solution of α-benzoin oxime with an aqueous solution of molybdenum in the oxidation state VI was investigated at two pH values (1 and 2.5) and for different values of the ligand/metal ratio. Depending on the experimental conditions, the reaction of α-benzoin oxime (H2L1) (C6H5(CHOH)-(C˭NOH)C6H5) with molybdenum(VI) leads to the formation of various complexes: (1) A white monomeric coordination complex of the formula [MoO2(HL1)2].H20. (2) A white dimeric coordination complex of the formula Mo2O5(HL2)2(L2)2].H2O in which, L2 is the deprotonated oxidized form of α-benzoin oxime, C6H5(C˭0)(C˭NO)C6H5. (3) A white dimeric coordination complex of the formula [Mo2O5(L2)2(HL3)2] in which HL3 is the hydrolyzed form of α-benzoin oxime, C6H5(C˭0)(CHOH)C6H5.

Reactivity of α-Benzoin Oxime with Vanadium: Synthesis and Characterization of Vanadium Coordination Compounds and Polyoxovanadate Adducts

The reactivity of an ethanolic solution of α-benzoin oxime with an aqueous solution of vanadium in the V, IV or III oxidation states was investigated for different values of pH (2–4.5) and different values of the ligand/metal ratio. Under these experimental conditions, the reaction of α-benzoin oxime (H2L1) with vanadium(V) leads to the formation of various compounds: (1) A dimeric coordination complex of the formula [V2O4(H2L1)2(L2)2].3H2O in which L2 is C6H5(C˭O)(C˭NO′)C6H5, the deprotonated oxidized form of α-benzoin oxime. (2) An orange-yellow decavanadate adduct of the formula Na5[HV10O28(H2L1)2(HL2)2].6H2O. (3) A green mixed-valence decavanadate adduct of the formula Na6[H5V10O28(HL2)6]·10H2O. In all these compounds, ligand-metal redox reactions take place at room temperature which progressively lead to a reduction of vanadium(V) to vanadium(IV). Only one dimeric vanadium(IV) coordination compound of the formula [V2O4(HL2)4].0.5H2O was isolated. The reaction of a-benzoin oxime with vanadium(EI) leads to a dimeric coordination complex of vanadium(IV) of the formula [V2O4(H2O)2(L4)4] in which α-benzoin oxime was transformed to dibenzil (L4) after hydrolysis and oxidation. Under inert atmospher (nitrogen), α-benzoin oxime does not form any complex with vanadium(III). It was hydrolysed to benzoin (HL3), vanadium(III) being the catalyst of the reaction.