Uranyl Schiff Base Complexes Research Articles

Role of Redox-Inactive Metal Ions in Modulating the Reduction Potential of Uranyl Schiff Base Complexes: Detailed Experimental and Theoretical Studies.

A mononuclear uranyl complex, [UO2L] (1), has been synthesized with the ligand N,N'-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane (H2L). The complex showed a reversible U(VI)/U(V) redox couple in cyclic voltammetric measurements. The reduction potential of this couple showed a positive shift upon the addition of redox-inactive alkali- and alkaline-earth Lewis acidic metal ions (Li+, Na+, K+, Ca2+, Sr2+, and Ba2+) to an acetonitrile solution of complex 1. The positive shift of the reduction potential has been explained on the basis of the Lewis acidity and internal electric-field effect of the respective metal ions. The bimetallic complexes [UO2LLi(NO3)] (2), [UO2LNa(BF4)]2 (3), [UO2LK(PF6)]2 (4), [(UO2L)2Ca]·(ClO4)2·CH3CN (5), [(UO2L)2Sr(H2O)2]·(ClO4)2·CH3CN (6), and [(UO2L)2Ba(ClO4)]·(ClO4) (7) have also been isolated in the solid state by reacting complex 1 with the corresponding metal ions and characterized by single-crystal X-ray diffraction. Density functional theory calculations of the optimized [UO2LM]n+ complexes have been used to rationalize the experimental reduction and electric-field potentials imposed by the non-redox-active cations.

Synthesis of new nano Schiff base complexes: X-ray crystallography, thermal, electrochemical and anticancer studies of nano uranyl Schiff base complexes

This study presents synthesis and characterization of new nano uranyl Schiff base complexes. Electrochemistry of these complexes showed a quasireversible redox reaction without any successive reactions. Furthermore, X-ray crystallography exhibited that beside the coordination of tetradentate Schiff base, one solvent molecule (dimethylformamide) was also coordinated. According to Coats-Redfern plots the kinetics of thermal decomposition of the studied complexes was first-order in all stages. Anticancer activities of the uranyl Schiff base complexes against cancer cell lines (Jurkat) was studied and determined by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazoliumbromide) assay. The results demonstrated that the complexes with aliphatic bridging units showed less anticancer activities than those having the aromatic units. KEY WORDS: Uranyl Schiff base complex, Anticancer activities, Thermal studies, Electrochemistry; X-ray crystallography Bull. Chem. Soc. Ethiop. 2018, 32(1), 89-100DOI: https://dx.doi.org/10.4314/bcse.v32i1.8

Sonochemical, spectroscopic study and antibacterial activity of two uranyl Schiff base complexes in nano scale

In this work, sonochemical method is applied for synthesis of two uranyle Schiff base complexes in nano scale. The complexes are characterized by FT-IR, 1HNMR, XRD, FESEM, UV–Vis and fluorescence analyses. Its spectral and antibacterial properties compared to bulk corresponding samples that exhibit a slight shift toward to the bulk corresponding samples due to reduce particle size. Synthesized complexes have a good antibacterial activity against Gram positive, bacteria (S. aureus, M. luteus, B. cereus and E. faecalis) and C. albicans yeast. Morphology of the complexes is rods that are different from bulk samples related to type of synthetic method. Sonochemical method able advanced coordination reaction in a short time with improved yields. In addition, this method has more advantages, such as environment-friendly and safety of the process.

Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

Uranyl(VI) complexes, [UO2(X-saloph)(solvent)], where saloph denotes N,N’-bis(salicylidene)-1,2-phenylenediamine and X = NO2, Cl, Me, H; were synthesized and characterized by 1H NMR, IR, UV–Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO2(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO2(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.

Uranyl Schiff base complexes as new heterogeneous catalysts for halogen exchange reactions between alkyl halides and elemental halogens

Mild and effective procedure for the halogen exchange reaction of alkyl halides with elemental iodine and bromine catalyzed with uranyl Schiff base complexes in various aprotic solvents was developed. Corresponding alkyl bromides and iodides were obtained with high yields within 20—70 min. The structures of the target products were confirmed by physical and spectroscopic data.

Synthesis, spectral characterization, structural studies, molecular docking and antimicrobial evaluation of new dioxidouranium(vi) complexes incorporating tetradentate N2O2Schiff base ligands

Two new uranyl(vi) Schiff base complexes were synthesized and characterized by physicochemical and spectroscopic methods. The antimicrobial activities of these complexes were also investigated against microorganisms.

Kinetics of Thermal Decomposition and Kinetics of Substitution Reaction of Nano Uranyl Schiff Base Complexes

This study focuses on the synthesis, characterization, and kinetics of substitution reaction of new uranyl Schiff base complexes prepared in a crystalline state as well as in a form of nanoparticles with sizes ranging between 35 and 60 nm. Preliminary Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) measurements indicated no difference between the two forms. The compounds were characterized by UV–vis, 1H NMR, cyclic voltammetry, X-ray crystallography, FTIR, TG, and CHN analyses. X-ray crystallography revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. Cyclic voltammetry of the complexes in acetonitrile revealed the quasi-reversible redox reaction. The TG and analysis of Coats–Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first order in all stages. The study of the kinetics and the mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was performed by the spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters revealed an associative mechanism for all corresponding complexes. Anticancer activity of the nano uranyl Schiff base complexes against cancer cell lines (Jurkat) was studied and determined by the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl-tetrazoliumbromide) assay.

New method in synthesis of nano uranyl(VI) Schiff base complexes: Characterization and electrochemical studies

This study presents a new method in synthesis of nano uranyl Schiff base complexes. In this method slow addition of dilute uranyl(VI) acetate solution to dilute Schiff base solution following the reflux for about 24h, yields nano uranyl(VI) Schiff base complexes. Characterization of Schiff base ligands and nano uranyl complexes has been done using 1H NMR, IR, UV–vis spectroscopy, elemental analysis. Schiff base ligands were synthesized by the condensation of one mole 3,4-diaminobenzophenone and two moles salicylaldehyde or substituted salicylaldehyde (3-OMe, 4-OMe, 5-OMe, 5-Br, 5-Cl). The electrochemical properties of the uranyl(IV) complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, according to the following trend: 5-MeO<H<5-Br≈5-Cl. Also the effect of the position of the substituted groups of Schiff base on the anodic potentials is as follows: 5-OMe<3-OMe<4-OMe.

Kinetic Studies of the Ligand Substitution Reaction of Some New Uranyl Schiff Base Complexes with Tri‐n‐butylphosphine

ABSTRACTKinetics of the substitution reaction of solvent molecule in uranyl(VI) Schiff base complexes by tri‐n‐butylposphine as the entering nucleophile in acetonitrile at 10–40°C was studied spectrophotometrically. The second‐order rate constants for the substitution reaction of the solvent molecule were found to be (8.8 ± 0.5) × 10−3, (5.3 ± 0.2) × 10−3, (7.5 ± 0.3) × 10−3, (6.1 ± 0.3) × 10−3, (13.5 ± 1.6) × 10−3, (13.2 ± 0.9) × 10−3, (52.9 ± 0.2) × 10−3, and (88.1 ± 0.6) × 10−3 M−1 s−1 at 40°C for [UO2(Schiff base)(CH3CN)], where Schiff base = L1–L8, respectively. In a temperature dependence study, the activation parameters ΔH# and ΔS# for the reaction of uranyl complexes with PBu3 were determined. From the linear rate dependence on the concentration of PBu3, the span of k2 values and the large negative values of the activation entropy, an associative (A) mechanism is deduced for the solvent substitution. By comparing the second‐order rate constants k2, it was concluded that the steric and the electronic properties of the complexes were important for the rate of the reactions.

Synthesis, characterization, anticancer activity, thermal and electrochemical studies of some novel uranyl Schiff base complexes

Some tetradentate N2O2 Schiff base ligands, such as N,N′-bis(naphtalidene)-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-methyl-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-chloro-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-nitro-1,2-phenylenediamine, N,N′-bis(naphtalidene)-4-carboxyl-1,2-phenylenediamine, and their uranyl complexes were synthesized and characterized by 1H NMR, IR, UV–Vis spectroscopy, TG (thermogravimetry), and elemental analysis (C.H.N.). Thermogravimetric analysis shows that uranyl complexes have very different thermal stabilities. This method is used also to establish that only one solvent molecule is coordinated to the central uranium ion and this solvent molecule does not coordinate strongly and is removed easier than the tetradentate ligand and also trans oxides. The electrochemical properties of the uranyl complexes were investigated by cyclic voltammetry. Electrochemistry of these complexes showed a quasireversible redox reaction without any successive reactions. Also, the kinetic parameters of thermal decomposition were calculated using Coats–Redfern equation. According to Coats–Redfern plots the kinetics of thermal decomposition of the studied complexes is first-order in all stages. Anticancer activity of the uranyl Schiff base complexes against cancer cell lines (Jurkat) was studied and determined by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazoliumbromide) assay.

Kinetic Studies of Substitution Reactions of Uranyl(VI) Schiff Base Complexes with Tributylphosphine

AbstractThe kinetics of the substitution reaction of uranyl Schiff base complexes with tributylphosphine was studied spectrophotometrically in acetonitrile. Uranyl complexes have a pentagonal bipyramidal structure with a trans‐UO2 moiety at the axial positions. In uranyl tetradentate Schiff base complexes, the fifth position of the equatorial plane is occupied by the solvent molecule, which weakly coordinates to the U center. In a substitution reaction, tributylphosphine can easily replace the solvent molecule. By considering the excellent linearity of kobs versus the molar concentration of tributylphosphine, the large negative values of Δ S#, and the small values of Δ H#, an associative (A) mechanism has been suggested. By comparing the rate constants (k2) and the activation parameters, it is obvious that two parameters are effective in the rate of substitution reactions; The first parameter is the steric effect that the rate of reaction has been decreased by increasing this factor, and the other parameter is the electronic property that the electron‐withdrawing group leads to increase the rate of reaction and the electron donor group decreases it. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 168–174, 2013

Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes

Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV–Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible.

A novel binuclear uranyl(VI) complex of bis(N,N′-3-carboxysalicylidene)-1,3-diaminopropan-2-ol: Synthesis, structure, and properties

A binuclear uranyl(VI) Schiff base complex of general formula [(UO2)2(H2L)(OH)(DMSO)2] · 2DMSO (I) (H2L = trianion of bis(N,N′-3-carboxysalicylidene)-1,3-diaminopropan-2-ol) was synthesized and studied by 1H NMR, UV-Vis, IR spectroscopy and X-ray crystallography.

Cation–Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

Three new cation-cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO(2)py(5))(KI(2)py(2))](n) (1) with the Schiff base ligands salen(2-), acacen(2-), and salophen(2-) (H(2)salen = N,N'-ethylene-bis(salicylideneimine), H(2)acacen = N,N'-ethylenebis(acetylacetoneimine), H(2)salophen = N,N'-phenylene-bis(salicylideneimine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen(2-) in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetranuclear complexes, {[UO(2)(acacen)](4)[μ(8)-](2)[K([18]C-6)(py)](2)} (3) and {[UO(2)(acacen)](4)[μ(8)-]}⋅2 [K([222])(py)] (4), {[UO(2)(salophen)](4)[μ(8)-K](2)[μ(5)-KI](2)[(K([18]C-6)]}⋅2 [K([18]C-6)(thf)(2)]⋅2 I (5), and {[UO(2)(salen)(4)][μ(8)-Rb](2)[Rb([18]C-6)](2)} (9) ([222] = [222]cryptand, py = pyridine), presenting a T-shaped cation-cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetranuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U(V)O(2)(salen)(py)][Cp*(2)Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation-cation complexes. The nature of the cation plays a key role in the preparation of stable cation-cation complexes. Stable tetranuclear complexes form in the presence of K(+) and Rb(+), whereas Li(+) leads to disproportionation. A new uranyl-oxo cluster was isolated from this reaction. The reaction of [U(V)O(2)(salen)(py)][Cp*(2)Co] (Cp* = pentamethylcyclopentadienyl) with its U(VI) analogue yields the oxo-functionalized dimer [UO(2)(salen)(py)](2)[Cp*(2)Co] (8). The reaction of the {[UO(2)(salen)(4)][μ(8)-K](2)[K([18]C-6)](2)} tetramer with protons leads to disproportionation to U(IV) and U(VI) species and H(2)O confirming the crucial role of the proton in the U(V) disproportionation.

Hydroxy- and alkoxy-bridged dinuclear uranyl–Schiff base complexes: hydrolysis, transamination and extraction studies

The reaction of uranyl nitrate with 1,3-bis(salicylideneamino)-2-propanol (H(3)L1) and 1,3-bis(3,5-di-tert-butylsalicylideneamino)-2-propanol (H(3)L2) in the presence of triethylamine (Et(3)N) yielded hydroxy- and alkoxy-bridged dinuclear complexes; [(UO(2))(2)(L1)(OH)(MeOH)(2)].(MeOH)(2) (.(MeOH)(2)) and [(UO(2))(2)(L2)(OH)(MeOH)(2)].(MeOH)(2) (.(MeOH)(2)). The crystal structures of .(DMF)(2) and .(DMF)(2) exhibit an unsymmetrical central U(2)O(2) core involving bridging alkoxy- and hydroxy-oxygen atoms. The geometry around the uranium center in .(DMF)(2) and .(DMF)(2) is that of a distorted pentagonal bipyramid with the solvent molecule occupying the fifth coordination site. The flexible nature of the ligand backbone is more pronounced in .(DMF)(2) compared to .(DMF)(2), yielding two molecules per unit cell in different conformations. Under similar reaction conditions, using ethylenediamine as a base, the respective Salen-based uranyl compounds, [UO(2)(Salen)(MeOH)] () and [UO(2)(Bu(t)(2)-Salen)(MeOH)] () are obtained due to transamination of the ligand backbone. Complexes .(MeOH)(2) and .(MeOH)(2) when reacted with an excess of ethylenediamine failed to yield the respective Salen-based complexes, and , respectively. The new compounds have been characterized using solution (NMR and UV-Vis) and solid-state (IR, X-ray crystallography) techniques. Hydrolysis of .(MeOH)(2) and .(MeOH)(2) in the pH range 1-14 was studied using UV-Vis spectroscopy and compared with the hydrolysis of and [UO(2)(Salophen)(MeOH)] (). A two-phase extraction study suggests quantitative removal of uranyl ions from the aqueous phase at higher pH conditions.

Uranyl stabilized Schiff base complex

Uranyl Schiff base complex [(UO(2))(2)(Salpro)(OH)(Solvent)(2)] (1) in the presence of excess of ethylenediamine (EDA) does not undergo nucleophilic addition (hydrolysis) and substitution (transamination) reactions due to an extended chelation [2N, 3O + OH] by the flexible backbone.

Contrasting Solvent and Capping Ligand Effects Directing the Photochemistry of Uranyl(VI) Schiff Base Complexes

Photolysis of the uranyl(VI) Schiff base complex UO2(tBu4-salphen)(THF) (1a) with cobaltocene in THF affords [Cp2Co][UO2(tBu4-salphen)(OH)] (2) in high yield while irradiation in toluene yields no reaction. Electronic emission spectra of 1a reveal a large Stokes' shift in toluene similar to that observed in the free ligand, while in THF the structural rearrangement responsible for this shift is blocked. Instead, the ligand-centered excited state is redirected to the uranyl(VI) center by way of energy transfer, thus generating 2 from the intramolecular activation of a coordinated THF molecule.

Immobilization of Uranyl Schiff Base in Mesoporous MCM-41

A uranyl Schiff base complex [UO2{ OC6H4N = C(H)C6H4O} ⋅H2O] has been immobilized inside the periodic mesopore channels of MCM-41 by the impregnation route. The samples have been characterized by XRD, N2 adsorption/desorption, TG-DTA, DR UV-vis, 29Si MAS NMR and FTIR techniques. While the host is found to retain its structural integrity, the surface area and the pore volume decrease considerably as a result of the intrapore confinement of complex molecules. The spectroscopy results indicate that the complex molecules are anchored with the silanol groups of MCM-41 via hydrogen bonding.

Molecular distortion in some solvates of uranyl Schiff's base complexes

Molecular distortion in some solvates of uranyl Schiff's base complexes

Synthesis and x-ray characterization of a uranyl(VI) Schiff base complex derived from a 2:2 condensation product of 3,4-diethylpyrrole-2,5-dicarbaldehyde and 1,2-diamino-4,5-dimethoxybenzene

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and x-ray characterization of a uranyl(VI) Schiff base complex derived from a 2:2 condensation product of 3,4-diethylpyrrole-2,5-dicarbaldehyde and 1,2-diamino-4,5-dimethoxybenzeneJonathan L. Sessler, Tarak D. Mody, and Vincent LynchCite this: Inorg. Chem. 1992, 31, 4, 529–531Publication Date (Print):February 1, 1992Publication History Published online1 May 2002Published inissue 1 February 1992https://doi.org/10.1021/ic00030a001RIGHTS & PERMISSIONSArticle Views670Altmetric-Citations90LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (294 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts