Ion exchangers as catalysts. II. Catalytic decomposition of hydrogen peroxide with resin-ethylenediamine-copper(II) complex ions

Summary The slow decomposition of H₂O₂ in the presence of Dowex-50 W resin in the form of an ethylenediaminecopper(II) complex ion in water is accompanied by an induction period. The reaction is first order with respect to [H₂O₂] and the rate constant (perg of dry resin) was deduced. Autocatalytic behaviour was found for the H₂O₂ decomposition with 2% crosslinked divinylbenzene. The induction period disappeared and the reaction rate increased when the decomposition was carried out with a resin in the form of a peroxo-copper complex, which proves that the formation of an intermediate (active species) retards the reaction rate. The precursor of the active species, formed during the induction period, was not the amine-copper(II) complex ion but a product of the latter with H₂O₂. It proved impossible to carry out the decomposition in acid or buffer solutions, in which the resin is regenerated.     

Compositional and 2H NMR studies of bis(benzene)chromium composites of mesoporous vanadium-niobium mixed oxides

New mesoporous niobium oxides with 5, 10, and 15 mol% vanadium(V) doped into the walls of the structure were synthesized by the ligand-assisted templating method with an octadecylamine template. These materials were characterized by XRD, XPS, EPR, elemental analysis, and nitrogen adsorption before being treated with excess bis(benzene)chromium to give new composites with an organometallic phase in the walls. All materials were also characterized by EPR, XRD, nitrogen adsorption, XPS, SQUID magnetometry, and elemental analysis. The materials with higher percentages of vanadium absorbed more bis(benzene)chromium, because this process depends largely on the electron transfer between the organometallic and the walls of the mesostructure and vanadium(V) is a stronger oxidant than niobium(V). Conductivity studies on these materials revealed that the ratio of Cr(0) to Cr(l) in the pores was more important than the absolute Cr loading level in governing electron transport properties but that increasing the V content led to more insulating behavior regardless of the Cr concentration. Solid-state 2H NMR studies on perdeuteriobenzene analogues of these composites showed the presence of the neutral and cationic Cr species in different ratios depending on the loading. Tumbling of these species was also slow on the NMR time scale, indicating that the charge-carrying Cr species are not rapidly moving through the pore channels of the mesostructure. This suggests that the walls of the structure may play a key role in charge transfer in these composites, contrary to what was previously believed.     

Study of support effects on the reduction of Ni2+ ions in aqueous hydrazine

We have studied the effect of silica of quartz-type on the reducibility of nickel acetate in aqueous hydrazine (80 degrees C, pH = 10-12) and metal particle formation. The obtained materials were characterized by X-ray diffraction, transmission electron microscopy, and thermodesorption experiments. With nickel acetate alone, the reduction was partial (45%) and a metal film at the liquid-gas interface or a powdered metal precipitate with an average particle size of 120 nm was obtained. In the presence of silica as the surfactant, the reduction of nickel acetate was total and the nickel phase deposited as a film on the support with an average particle size of 25 nm. Supported nickel acetate was also totally reduced. Crystallites of a mean particle size of about 3 nm were obtained. Decreasing the nickel content or increasing the hydrazine/nickel ratio decreased the metal particle size. Whiskers were formed for low nickel loadings. Hydrogen thermal treatment of the reduced phase showed that the organic acetate fragment, belonging to the precursor salt, still remained strongly attached to the nickel phase. The amount of the retained organic matrix depended on the metal particle size. Surface defects are suggested as active sites, which enhanced nickel ion reduction in the presence of silica as the surfactant or support. Metal-support interactions and the nucleation/ growth rate were the main factors determining the size and morphology of the supported metal particles formed. The organic matrix covered the reduced nickel phase.     

Geometric molecular similarity from volume-based distance minimization: Application to saxitoxin and tetrodotoxin

The geometric molecular dissimilarity between two molecules is defined as the difference between the volume of their union minus the volume of their intersection. This dissimilarity has the mathematical properties of a distance. This distance is minimized under all rotations and translations using a discrete Broyden, Fletcher, Goldfarb & Shanno (B.F.G.S.) algorithm. The optimal geometric superimposition of saxitoxin and tetrodotoxin is discussed. © 1995 by John Wiley & Sons, Inc.     

A new route to vinyltributyltin compounds by flash pyrolysis of alkyltributyltin acetates

Flash pyrolysis of alkyltributyltin acetates, at high temperatures (600–850° C) under a moderate vacuum provides a convenient route to vinyltin derivatives.     

Mechanical and physico-chemical characterization of cyclodextrin finished polyamide fibers

We present the study of the cyclodextrin (CDs) finishing of polyamide fibers (PA) by means of citric acid (CTR) as crosslinking agent. We observed that the mode of grafting happened by the formation of a crosslinked polymer formed between CTR and CDs. This polymer physically adhered to the fibers network and was resistant to hot water washings. Modified fibers were characterized by evaluating the contact angle with a polar liquid and by studying the hysteresis of damping of PA fibers (Cahn balance) with various grafting rates and by studying the absorptivity of grafted fabrics via the technique of the posed drop (Digidrop^® instrument). Then a mechanical characterization of the PA fabrics grafted with various proportions of CDs was accomplished, by traction and tear tests by using a tensile-test bench Lohmergy. Finally a topographic study of PA grafted surfaces was approached by atomic force microscopy (AFM and LFM; contact and non-contact mode) which permitted to evaluate the roughness and the chemical heterogeneity of the grafted surfaces.     

Scope, limitations and mechanistic aspects in the selective homogeneous palladium-catalyzed reduction of alkenes under transfer hydrogen conditions

A new and efficient mild Pd/P(t-Bu)₃ catalyst for selective reduction of various alkenes under transfer hydrogen conditions has been developed leading to the corresponding saturated derivatives in chemical yields varying from 65 to 98%. Mechanistic rationale of this reaction has been also demonstrated.     

Magic numbers in the mass distribution of the benzene+-argonn ions: evaporation dynamics and cluster structure

The intensity distribution of benzene⁺-Ar_n cluster ions formed by laser ionization of neutral clusters has been investigated: two main intensity anomalies (magic numbers atn=20 and 45) have been observed in the 15–60 size range. The evaporation dynamics of these species in the 2–50 microsecond time window following ionization has been studied using the electrostatic mirror of a reflectron time-of-flight mass spectrometer as a kinetic energy analyser capable to distinguish parent and daughter ions. The magic numbers are interpreted in terms of size dependent evaporation behaviors: beyondn=20, a sudden decrease of the evaporation energy is observed; in then=45–47 size range, the magic number is accounted for by the specific dynamics of then=46 and 47 clusters, in particular the possible loss of two argon atoms forn=47 within the experimental time window. These results and their implications on the cluster structure are discussed in the light of the evaporative ensemble model and compared to the evaporation characteristics of similar species, in particular the neat rare gas clusters.     

Ester interchange reactions catalyzed by tin compounds in reactive processing: NMR contribution via reactions with model compounds

Interchange reactions involving esters were used in reactive processing with a view to obtaining polymer blends with stabilized morphology. Dibutyltinoxide (DBTO) appeared to be an excellent catalyst for these reactions. In fact, it was shown that the true catalytic entity is a dimeric alkoxy, acyloxy distannoxane entity formed in situ, during processing, by the reaction of the DBTO with the polymer ester groups. This compound was first obtained with model esters and characterized by multinuclear NMR analysis (¹H, ¹³C, ¹¹⁹Sn). The catalytic efficiency of the in situ polymeric distannoxane was compared with other added parent distannoxanes. Later on – still with model compounds – ligand exchanges at the tin sites were investigated and it was shown that these exchanges are not essential to the catalyst activity, but when they take place it increases the catalytic efficiency. Then, this type of catalysis was successfully used for interchange reactions in reactive extrusion of different polymer blends, some applications are briefly presented. To cite this article: M.-F. Llauro and A. Michel, C. R. Chimie 9 (2006).     

Diterpenoids from cultured Erythropodium caribaeorum

The known antimitotic agent eleutherobin and the briarane diterpenoids erythrolides A and B have been isolated from cultured specimens of Erythropodium caribaeorum in amounts comparable to those reported from wild-harvested reef animals. The novel diterpenoid aquariolide A, having an unprecedented highly rearranged carbon skeleton (named aquariane), has also been found. The aquariane skeleton can be formally derived from the briarane skeleton by sequential di-pi-methane and vinyl-cyclopropane rearrangements. [structure: see text]