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X-ray absorption fine structure study of the bound state electronic transitions at the vanadium K and L edges in low symmetry, molecular, vanadium-(IV) and -(V) complexes with oxyoxime and oxyoximate ligands

A combination of vanadium K- and L-edge XAFS has been used to characterise a series of monomeric oxovanadium(IV), monomeric dioxovanadium(V) and dimeric oxovanadium(V) complexes with oxyoxime and oxyoximate ligands. The K- and L-edge spectra confirm the presence of VV in the dimeric species and the L-edge spectra have been used to discriminate between six-co-ordinate V-N-O-V bridged oxovanadium(V) dimers and seven-co-ordinate phenolate bridged oxovanadium(V) dimers containing eta2-N-O groups.

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Metal catalyst and ligand design,
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Synthesis, structures and reactivity of two oxidovanadium(IV) and dioxidovanadium(V) selenosemicarbazonato complexes

The preparation as well as spectroscopic and structural characterization of some oxovanadium(IV) and dioxovanadium(V) complexes containing deprotonated selenosemicarbazone ligands is reported.

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Metal catalyst and ligand design,
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Synthesis and structural characterization of oxovanadium(IV) complexes of dimedone derivatives

We have successfully synthesized new oxovanadium (IV) complexes with dimedone derivatives and their structure were confirmed by elemental analyses, spectroscopic techniques (FT-IR, UV?visible, EPR) and thermal analysis. The reaction of [VO (acac)2] with the azo dimedone ligands (HLn) produced mononuclear oxovanadium (IV) complexes with formula [VO (Ln)2]H2O. Results of the molar conductance proved that VO2+ complexes are non-electrolytes and fall in the range 14?16 Omega-1cm2mol?1. The coordination geometry of VO (IV) complexes is square-pyramidal, where vanadium (IV) ion is coordinated by oxygen atom of the carbonyl (C=O) group, and nitrogen atom of the deprotonating hydrazone moiety (?NH?), while the fifth position is occupied by an oxo group. Moreover, the optimized structure, bond angles, bond lengths, as well as the calculated quantum chemical parameters of the complexes have been estimated. DNA binding activities of the complexes were investigated using electronic absorption titration and viscosity measurements. The obtained results showed groove binding of the complexes to CT-DNA accompanied with a partial insertion of the ligand between the base stacks of the DNA with a binding constant of 2.07?5.51 x 105 M?1 range. Evaluation results of the synthesized complexes against the human cancer cell lines HepG-2 and MCF-7, as compared to the positive controls in the viability assay of vinblastine and colchicine have been reported. The in vitro anti-oxidant activity of all the complexes is determined by DPPH free radical-scavenging assay. Finally, the anti-microbial activities of the complexes have been investigated against fungal (Candida albicans), gram negative bacteria (Escherichia coli), and gram positive bacteria (Staphylococcus aureus) using the disc-diffusion method.

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Metal catalyst and ligand design,
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Ag2O-decorated electrospun BiVO4 nanofibers with enhanced photocatalytic performance

Semiconductor photocatalysts are emerging as tools for pollutant degradation in industrial wastewater, air purification, antibacterial applications, etc. due to their use of visible light, which is abundant in sunlight. Here, we report a new type of p-n junction Ag2O/BiVO4 heterogeneous nanostructured photocatalyst with enhanced photocatalytic performance. P-type Ag2O nanoparticles were in situ reduced and assembled on the surface of electrospun BiVO4 nanofibers using ultraviolet (UV) irradiation; this process hindered the recombination of localized photogenerated electron-hole pairs, and hence resulted in the enhanced photocatalytic activity of the BiVO4/Ag2O nanocomposites. The photocatalytic activities of the obtained BiVO4 and BiVO4/Ag2O nanocomposites were assessed by measuring the degradation of rhodamine B (RhB) under visible light. The 10 wt% Ag2O/BiVO4 sample yielded the optimum degradation of RhB (98.47%), much higher than that yielded by pure BiVO4 nanofibers (64.67%). No obvious change in the XRD pattern of an Ag2O/BiVO4 sample occurred as a result of its use in the photocatalytic reaction, indicating its excellent stability. The high photocatalytic performance observed was attributed to the large surface-to-volume ratio of the essentially one-dimensional electrospun BiVO4 nanofibers and to the in situ growth of p-type Ag2O on the surface of the n-type BiVO4 nanofibers.

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Metal catalyst and ligand design,
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A robust in vitro Anticancer, Antioxidant and Antimicrobial Agents Based on New Metal-Azomethine Chelates Incorporating Ag(I), Pd (II) and VO (II) Cations: Probing the Aspects of DNA Interaction

A novel azomethine ligand (HNAP) [HNAP = 1-(Pyridin-3-yliminomethyl)-naphthalen-2-ol] and its Ag(I), Pd (II) and VO (II) chelates have been synthesized and structurally inspected using a wide range of spectroscopic and analytical tools, including infra-red (IR), ultraviolet-visible (UV-Vis) and 1H NMR spectroscopy techniques, CHN analysis, molar conductance, magnetic susceptibility, and thermogravimetric analysis. The molar conductance measurements reveal that the chelates are non-electrolytes. The thermal behavior of the investigated metal chelates shows that the hydrated, coordinated water molecules and the anions are removed in successive steps followed immediately by decomposition of the ligand in the subsequent steps. The activation thermodynamic parameters are calculated from the TG curves and discussed. Complexes formation study via continuous variation m molar ratio has been investigated, and results were consistent to those found in the solid complexes with a ratio of (M:L) as (1:1) or 1:2 (M:L) molar ratio for all the monolithic and bi-valent metal complexes with square planar for Pd (II), and Ag(I) cations while, square pyramidal geometry for VO (II) cation. DFT calculations for the titled different metal-chelates have been studied and showed a good correlation with the experimental data. The prepared compounds had been checked In vitro towards numerous sorts of plant pathogenic fungi and bacteria to evaluate their antimicrobial properties and compared with some known antibiotics. Significantly, all the complexes show excellent antimicrobial activity against various strains of bacteria and fungi, including both Gram-negative and Gram-positive bacteria. Besides, the complexes exhibited high cytotoxicity against various carcinoma cell lines, including HCT-116, MCF-7, and HepG-2. Moreover, the effect of the new synthesized compounds as antioxidants was determined by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH) and compared with that of Vitamin C. Furthermore, the binding interactions of the complexes with CT-DNA were explored using UV-Vis spectroscopy, viscosity and gel electrophoreses measurements. They cooperatively bind to DNA possibly through intercalations. The binding ability of the complexes was shown as HNAPAg > HNAPPd > HNAPVO complex.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Oxidation of alkenes in supercritical carbon dioxide catalyzed by molybdenum hexacarbonyl

In supercritical CO2, olefin oxidation to epoxides or diols using a Mo(CO)6 catalyst precursor and using t-BuOOH as oxidant proceeds in nearly quantitative yields. The highest yields and fastest rates of diol and epoxide formation were observed with cis-alkenes, while trans-alkenes were considerably less reactive. Phenyl-substituted olefins show a tendency to cleave to their corresponding aldehyde. The use of 70 wt % aqueous solutions of tert-butyl hydroperoxide yield the trans-diol, while anhydrous decane solutions of t-BuOOH give the epoxide. Clearly Mo(CO)6 proved to be the most effective oxygen transfer catalyst for these reactions. Several other oxygen transfer catalysts were tested but proved to be less effective under these conditions. An autoclave equipped with quartz windows allowed for the qualitative determination of a homogeneous reaction environment in the supercritical fluid.

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Metal catalyst and ligand design,
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An oxo-bridged dinuclear vanadium(V) complex of N,N’-bis(salicylidene)-1,5- diimino-3-azapentane: Synthesis and structure

The reaction of vanadyl acetylacetonate with N,N’-bis (salicylidene)-1,5- diimino-3-azapentane (H2SDA) affords an oxo-bridged dinuclear Schiff base vanadium(V) complex, [VO2(HSDA)]2. The structure of the complex was characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. The complex crystallizes as monoclinic space group P21/n, with a = 6.619(2), b = 32.592(3), c = 8.715(2) A, beta = 104.001(3), V=1824.2(7) A3, Z=4, R1 =0.0637, wR2 =0.1228 for 1989 observed data. The complex exhibits a distorted octahedral geometry, involving in the equatorial plane the phenolate, imine, and amine donors of the Schiff base ligand and the bridging oxo O group and in the axial positions two other oxo O groups. The intramolecular V…V distance is 3.226(1) A. Copyright Taylor & Francis Group, LLC.

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Metal catalyst and ligand design,
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Periodic mesoporous organosilica incorporating a catalytically active vanadyl Schiff base complex in the framework

A vanadyl Schiff base complex having two terminal trimethoxysilyl groups peripheral to the ligand has been used to obtain a MCM-41-like mesoporous organosilicate that has been found to catalyze efficiently the cyanosilylation of carbonyl groups. Evidence for the successful preparation of the periodic mesoporous organosilica is based on powder XRD (high periodicity), isothermal Ar adsorption (900 m2/g), mono-modal pore-size distribution (42 A), diffuse reflectance UV-visible spectroscopy (characteristic absorption band of vanadyl salen complex), and 29Si NMR (presence of T3 silicon atoms, CH2-Si(OSi)3). In addition, we have been able to prepare a chiral vanadyl salen complex that is able to catalyze the carbonyl addition with 30% ee.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Hierarchical Composite of Rose-Like VS2@S/N-Doped Carbon with Expanded (001) Planes for Superior Li-Ion Storage

In the present work, a hierarchical composite of rose-like VS2@S/N-doped carbon (VS2@SNC) with expanded (001) planes is successfully fabricated through a facile synthetic route. Notably, the d-spacing of (001) planes is expanded to 0.92 nm, which is proved to dramatically reduce the energy barrier for Li+ diffusion in the composite of VS2@SNC by density functional theory calculation. On the other hand, the S/N-doped carbon in the composite greatly promotes the electrical conductivity and enhances the structural stability. In addition, the hierarchical structure of VS2@SNC facilitates rapid electrolyte diffusion and increases the contact area between the electrode and electrolyte simultaneously. Benefiting from the merits mentioned above, the VS2@SNC electrode exhibits excellent electrochemical properties, such as a large reversible capacity of 971.6 mA h g?1 at 0.2 A g?1, an extremely high rate capability of 772.1 mA h g?1 at 10 A g?1, and a remarkable cycling stability up to 600 cycles at 8 A g?1 with a capacity of 684.5 mA h g?1, making it a promising candidate as an anode material for lithium-ion batteries.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Syntheses, characterization, and crystal structures of oxovanadium(V) complexes with similar tridentate hydrazones

Reactions of bis(acetylacetonato)oxovanadium(IV) with N?-[2-hydroxy- 4-diethylaminobenzylidene)]-2-methylbenzohydrazide (H2HMB) and N?-[5-bromo-2-hydroxy-3-methoxybenzylidene)]-2-methylbenzohydrazide (H2BMB), respectively, produce two oxovanadium(V) species with the formulas [VO(OMe)(HMB)]2 (I) and [VO(OMe)(HOMe)(BMB)] (II). The complexes have been characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The crystal of I is triclinic: space group P betaar 1$, a = 8.843(1), b = 9.937(1), c = 12.327(2) A, alpha = 96.500(2), beta = 110.070(2), gamma = 104.220(2), V = 962.8(2) A3, Z = 1. The crystal of II is monoclinic: space group P21/c, a = 9.908(2), b = 19.968(3), c = 11.065(3), beta = 109.362(3), V = 2065.3(8) A3, Z = 4. Compound I is the methoxide-bridged dimeric oxovanadium(V) complex, and II is the mononuclear oxovanadium(V) complex. Each V atom in the complexes is in an octahedral coordination.

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Reference£º
Metal catalyst and ligand design,
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