Photodissociation of vanadium, niobium, and tantalum oxide cluster cations

Transition-metal oxide clusters of the form M(n)O(m) (+)(M=V,Nb,Ta) are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. Consistent with earlier work, cluster oxides for each value of n produce only a limited number of stoichiometries, where m>n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic of a Nd:YAG (yttrium aluminum garnet) laser. All of these clusters require multiphoton conditions for dissociation, consistent with their expected strong bonding. Dissociation occurs by either elimination of oxygen or by fission, repeatedly producing clusters having the same specific stoichiometries. In oxygen elimination, vanadium species tend to lose units of O(2), whereas niobium and tantalum lose O atoms. For each metal increment n, oxygen elimination proceeds until a terminal stoichiometry is reached. Clusters having this stoichiometry do not eliminate more oxygen, but rather undergo fission, producing smaller M(n)O(m) (+) species. The smaller clusters produced as fission products represent the corresponding terminal stoichiometries for those smaller n values. The terminal stoichiometries identified are the same for V, Nb, and Ta oxide cluster cations. This behavior suggests that these clusters have stable bonding networks at their core, but additional excess oxygen at their periphery. These combined results determine that M(2)O(4) (+), M(3)O(7) (+), M(4)O(9) (+), M(5)O(12) (+), M(6)O(14) (+), and M(7)O(17) (+) have the greatest stability for V, Nb, and Ta oxide clusters.     

Quantum-chemical study of quasi-one-dimensional vanadium and niobium sulfides with Peierls distortion

The electronic structure and lattice parameters of several quasi-one-dimensional compounds–known VS₄, NbCl₄, and NbS₃ and hypothetical NbS₄ and VS₃–are obtained using density functional theory. Comparative analysis of chemical bonding and charge distribution in all these compounds reveals the possible origin of the structural instability of NbS₄ and VS₃.     

Hydrogenation of nanostructured alloys and composites based on magnesium

The capability of sorbing hydrogen was studied for the magnesium alloys and related composites. The microstructures of the Mg-Ni binary eutectic alloys and Mg-La-Ni and Mg-Mm-Ni ternary eutectic alloys were studied. Both the initial alloys and alloys modified by the method of equal channel angular pressing were used as objects of the study. Features of interaction of the alloys with hydrogen were revealed. Sorption of hydrogen by the metal hydride composites based on alloys and ??pseudoalloys,?? viz., alloys obtained by sintering of mechanochemically treated highly dispersed powders formed by the hydride dispersion of metallic phases, was studied. Metal??carbon composites based on highly dispersed magnesium alloys or pseudoalloys and carbon nanostructures were formed, and the absorption of hydrogen by these composites was examined.     

Hydrogen sorbing magnesium alloys and composites

The authorsr works studying the hydrogen sorption properties of the magnesium-based materials are reviewed. The objects of the studies were highly dispersed powders of Mg—La—Ni and Mg—Mm—Ni alloys (Mm is misch metal) of the ternary eutectic, composites of magnesium alloys with extended carbon nanostructures, and composites of magnesium hydride with lanthanide oxides. The positive effect of lanthanide oxide additives on the process of hydro-gen desorption from magnesium hydride and the role of carbon nanofibers in these processes carried out at room temperatures are discussed.     

Recent advances in vanadium catalyzed oxygen transfer reactions

Vanadium complexes have proven to be effective catalysts for the activation of peroxides and the selective oxidation of substrates like bromides, sulfides and alkenes. Besides their capability to form metalloperoxo species, which effectively transfer oxygen atoms to the substrate, these systems are synthetically useful for obtaining valuable oxidized molecules on a preparative scale, with a high degree of selectivity and TONs. Furthermore, the use of environmentally friendly oxidants like hydrogen and alkyl hydroperoxides increases significantly their potential application at an industrial level.Here we report a critical survey on the most effective homogeneous vanadium catalysts reported in the last decade concerning their synthetic application in oxygen transfer reactions (sulfoxidation, epoxidation, haloperoxidation) using hydrogen peroxide or alkyl hydroperoxides, demonstrating the different classes of ligands and complexes, their catalytic performances, their reactivity, chemo, stereo and substrate selectivity. Some examples of the use of non conventional reaction media or techniques and catalyst recycling studies will be also discussed.     

Spectrophotometric determination of vanadium and niobium: Xylenol orange as a chromogenic reagent

Summary The formation of red coloured chelates of vanadium(V) and niobium(V) with xylenol orange (DCAC) having _max at 490 nm (at p_H 5.0) and 530 nm (at p_H 5.5) have been reported. The colour formation has been applied to the spectrophotometric determination of metal ions. The colour has been found to be stable between p_H 3.5–6.5 and 2.0–7.0 respectively. The sensitivity of the reagent is 0.051g/cm² of vanadium and 0.093g/cm² of niobium. Maximum colour intensity has been found for Nb-DCAC chelate at p_H 5.5 whereas no appreciable change has been found for V-DCAC chelate between p_H 4.5 and 6.5.

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Zusammenfassung Über die Bildung rot gefärbter Chelate von Vanadin und Niob mit Xylenolorange wurde berichtet. Deren Absorptionsmaxima liegen bei 490 nm (p_H 5,0) bzw. bei 530 nm (p_H 5,5). Die Farbreaktion wurde für die Bestimmung der beiden Metalle verwendet. Die Farbe ist zwischen p_H 3,5 und 6,5 bzw. zwischen p_H 2,0 und 7,0 stabil. Die Empfindlichkeit für Vanadin beträgt 0,051g/cm², für Niob 0,093g/cm². Die Farbe des Niobchelates erreicht bei p_H 5,5 ein Maximum, während die des Vanadinchelates zwischen p_H 4,5 und 6,5 keine wesentlichen Änderungen erkennen läßt.

     

Guanylation of aromatic amines catalyzed by vanadium imido complexes

The reaction of formation of guanidines by coupling of carbodiimides and aromatic amines using imido vanadium complexes as catalyst have been investigated. Results demonstrate that the complex V(N-2,6-ⁱPr₂C₆H₃)Cl₃ is an effective catalyst for this process.     

Fragmentation of sputtered vanadium and niobium cluster ions,kinetic release and dissociation energy

The generation and unimolecular fragmentation of V _n ⁺ and Nb _n ⁺ clusters formed in sputtering vanadium and niobium surfaces by Xe⁺ ions has been studied. The method of measuring the kinetic energy of fragment ions (kinetic energy release distribution) has been used to determine the dissociation energy. Kinetic energy spectra have been measured in the field-free zone (corresponding to a time window of 10⁻⁵–10⁻⁴ sec after emission) of an ion microanalyzer with double focusing in reverse geometry. The results of spectra measurement were treated using the Rice-Ramsperge-Kassel theory of unimolecular reactions and the “evaporative ensemble”, which allowed us to calculate the dissociation energies of homonuclear V _n ¹ (n= 5–11) and Nb _n ¹ (n = 3–8) clusters.     

Aerobic oxidation of organic compounds catalyzed by vanadium compounds

Aerobic oxidation of α-hydroxy ketones catalyzed by dichloroethoxyoxovanadium in ethanol causes a carbon–carbon bond cleavage that produces diesters or diketones. This reaction is highly chemoselective, and disecondary glycols do not react at all. However, ditertiary glycols effectively react with dichloroethoxyoxovanadium or trichlorooxovanadium to provide the corresponding ketones. Aerobic oxidation of α-hydroxy ketones catalyzed by dichloroethoxyoxovanadium or trichlorooxovanadium in aprotic solvents almost quantitatively affords the corresponding α-diketones. The reaction of tertiary cyclopropanol compounds with vanadyl acetylacetonate under an oxygen atmosphere causes fragmentation of the cyclopropane moiety to produce β-hydroxy ketones and β-diketones. For the 6-substituted bicyclo[4.1.0]heptanol derivatives, the endoperoxides are also obtained together with β-hydroxy ketones. Conversely, 2-ethoxycarbonylcyclopropyl silyl ethers produce γ-oxocarboxylate derivatives given the same reaction conditions. Monothioacetals are easily deprotected into carbonyls using a catalytic amount of trichlorooxovanadium in 2,2,2-trifluoroethanol under an oxygen atmosphere. Thiols are converted into the corresponding disulfides by the aerobic oxidation catalyzed by trichlorooxovanadium in the presence of molecular sieves 3A. Polymer-supported vanadium compounds are synthesized by the reaction of vanadium oxytrichloride with polymers bearing hydroxyl moieties. The catalyst prepared from TentaGel S OH was highly active and reusable for the aerobic oxidations.     

XAS investigation of tantalum and niobium in nanostructured TiO2 anatase

Sol-gel routes were used to prepare Ta 10 at% and Nb 5 at% and 10 at% doped titania nanosized powders. When fired between 410°C and 850°C the doped titania powders are in the anatase phase; further heating up to 1050°C is required to obtain the rutile phase. The presence of dopant atoms delays the rate of transformation as compared with pure titania powders. Doping also affects the rate of grain growth and increases the conductance response to gas. To better understand the role played by dopant atoms in inhibiting both phase transformation to rutile and grain growth, X-ray Absorption Spectroscopy measurements were performed at the L_III-L_I absorption edges of Ta and Nb K absorption edge. Analysis was restricted to the anatase phase because the transformation to rutile phase, obtained by firing at 1050°C, is accompanied by the formation of undesired Ta and Nb oxides (Ta₂O₅ and Nb₂TiO₇, respectively). Extended X-ray Absorption Fine Structure and X-ray Absorption Near-Edge Spectroscopy analysis results indicate that in nanostructured anatase both tantalum and niobium atoms substitute Ti cations with +5 valence state.     

Ion-exchange separation of vanadium, zirconium, titanium, molybdenum, tungsten and niobium

Schemes for the separation of two or more of the elements vanadium, zirconium and/or titanium, molybdenum and tungsten from each other and from relatively large amounts of niobium have been developed, a strongly basic anion-exchange resin being used. Interference from niobium is avoided by using hydrofluoric acid to elute vanadium, zirconium, titanium and molybdenum. The application of coupled columns to improve the efficiency of separation of multicomponent mixtures is demonstrated. The use of an "interval" equation defining the volume interval between successively eluted solutes is proposed for calculating the column length required for a particular separation. This equation is especially useful for determining the extent to which a column must be lengthened when overlapping occurs because of high column loading.     

Nitrilation of carboxylic acids with acetonitrile catalyzed by molybdenum and vanadium complexes

Various carbonitriles were synthesized by reaction of the corresponding carboxylic acids with acetonitrile in carbon tetrachloride in the presence of VO(acac)₂ and Mo(CO)₆ in 6 h at 150–170°C.     

Polyaniline supported vanadium catalyzed aerobic oxidation of alcohols to aldehydes and ketones

Polyaniline supported vanadium complex 1 catalyzes efficiently the oxidation of alcohols to aldehydes and ketones in high yields under molecular oxygen in toluene at ca. 100 °C. The catalyst 1 can be recycled without loss of activity.     

Hydrogen bond catalyzed direct reductive amination of ketones

[reaction: see text] A novel, biomimetic concept for the direct reductive amination of ketones is described that relies on selective imine activation by hydrogen bond formation. The mild, acid- and metal-free process requires only catalytic amounts of thiourea as hydrogen bond donor and utilizes the Hantzsch ester for transfer hydrogenation. The method allows the efficient synthesis of structurally diverse amines.     

Hydrogen diffusion transfer through an asymmetric three-layer vanadium membrane

Hydrogen diffusion transfer through a three-layer membrane has been studied within the framework of the lattice model under the Bragg?Williams approximation. A set of equations describing hydrogen transfer through a vanadium membrane coated with thin palladium layers has been derived taking into account the interactions of hydrogen atoms in the membrane layers. The obtained equations have been solved using the Mathcad-14 software package. It has been shown that the interaction between hydrogen atoms has a significant influence on hydrogen permeability at near-atmospheric pressures. It has been found that the permeability of the vanadium membrane is markedly higher than that of a palladium one at the same thickness. The effect of asymmetric vanadium membrane embrittlement has been shown to depend on the location of palladium layers with different thicknesses. The embrittlement of the vanadium membrane begins at higher pressures, when a thicker palladium layer is located at the inlet. It has been revealed that, for asymmetric membranes, the value of the diffusion flux of hydrogen atoms may depend on the transfer direction. At the same membrane thickness, the permeability of the asymmetric membrane is actually equal to that of a symmetrical membrane, provided that a thicker palladium layer is located at the inlet. At the opposite orientation, of the permeability of the asymmetric membrane is lower than that of the symmetric one.     

Effect of deposition conditions on properties of nanostructured magnesium hydroxide powders

Change in the dispersity, microstructure, and adsorption properties of mesoporous magnesium hydroxide powders synthesized by the precipitation method from solutions upon introduction of surfactants and under the action of microwave and ultrasonic irradiation was studied. Highly dispersed nanostructured Mg(OH)₂ powders were obtained with average sizes of primary and secondary particles of, respectively, 13–27 and 180–383 nm. The specific surface area, pore volume, and average pore diameter of the samples under study varied, depending on the preparation conditions, within the ranges 86–98 m² g^–1, 0.491–0.737 cm³ g^–1, and 24–32 nm, respectively. It was shown that highly dispersed mesoporous magnesium hydroxide powders can be directionally synthesized by the precipitation method, which opens up wide opportunities for their application as nanoreactors for synthesis of nanosize isolated particles and development of poly-path catalysts on their basis.